High-strength aluminum-based alloy material and production process thereof
Patent Information
- Application Number
- PCT/CN2026/085049
- Authority / Receiving Office
- WO · WO
- Patent Type
- Applications
- Current Assignee / Owner
- Priority Date
- 2025-03-27
- Filing Date
- 2026-03-22
- Publication Date
- 2026-10-01
Smart Images
Figure PCTCN2026085049-APPB-I100001
Abstract
Description
A high-strength aluminum-based alloy material and its manufacturing process
[0001] This application is based on and claims priority to Chinese Patent Application No. 2025103685070, filed on March 27, 2025.
[0002] The entire contents of the above applications are incorporated herein by reference. Technical Field
[0003] This invention belongs to the field of aluminum alloy material technology, specifically relating to a high-strength aluminum-based alloy material and its production process. Background Technology
[0004] Aluminum alloys are alloys with aluminum as the base material and a certain amount of other alloying elements added. They are one of the light metal materials, with high strength, good casting and plastic processing properties, good electrical and thermal conductivity, good corrosion resistance and weldability. They can be used as structural materials and are applied in aerospace, aviation, transportation, construction, electromechanical, light chemical and daily necessities fields.
[0005] Currently, among the aluminum alloy materials suitable for mature additive manufacturing, only some Al-Si alloys and a very small number of Al-Mg alloys can be laser additively formed. However, Al-Si alloys suffer from insufficient material properties due to the influence of the material system and the inherent solid solubility of elements in aluminum alloys. While Al-Mg alloys have good strength, the high Mg content added during the forming process to achieve high strength leads to the formation of large amounts of volatile dust under laser bombardment. This high porosity affects the material's density, resulting in high-strength materials that are prone to fatigue instability, severely hindering their practical application. Furthermore, currently used Al-Mg alloys all employ Sc strengthening, i.e., the Al-Mg-Sc system, which involves expensive raw materials, further limiting their application.
[0006] Traditional preparation methods, such as improving alloy purity, adjusting composition, and modifying heat treatment specifications, are becoming increasingly less effective in developing new aluminum alloy materials. To significantly improve the strength, corrosion resistance, heat resistance, and fracture toughness of materials, aluminum alloy melt is atomized, rapidly solidified into powder, and then pressed, sintered, and pressure-processed into aluminum alloy materials. The resulting materials have fine grains, refined intermetallic compound particles, uniform chemical composition, and increased supersaturated solid solubility of alloying elements. This allows for the comprehensive utilization of dispersion strengthening, solid solution strengthening, and age-hardening effects, resulting in materials with high strength and excellent resistance to stress corrosion. However, currently produced aluminum alloy powders are primarily produced using inert gas atomization or centrifugal atomization, resulting in low particle dispersion and easy agglomeration. While lubricants and binders such as paraffin wax and zinc stearate are typically added to promote powder formation, this process introduces impurities into the aluminum alloy powder, affecting the material's strength. Summary of the Invention
[0007] In order to solve the technical problem of poor mechanical properties in related technologies, the purpose of this invention is to provide a high-strength aluminum-based alloy material and its production process.
[0008] To achieve the above objectives, the technical solution of the present invention is as follows:
[0009] In this article, "metal melt" refers to the molten aluminum-based alloy formed by heating and melting; "vacuum atomization" refers to the process of atomizing the metal melt with an inert gas as the atomizing medium in a vacuum atomization device, so that it can be rapidly solidified into powder; "nano-reinforcing agent" refers to zirconium oxide nanopowder, which forms a dispersed phase in the aluminum-based alloy matrix and plays a pinning role to improve mechanical properties.
[0010] A high-strength aluminum-based alloy material, comprising the following components by mass percentage:
[0011] Magnesium 1.0%-3.2%, zirconium 1.0%-2.7%, manganese 1.25%-1.53%, copper 0.8%-1.4%, vanadium 0.2%-0.5%, nano-reinforcing agent 0.7%-1.0%, and balance aluminum; the nano-reinforcing agent is zirconium oxychloride nanopowder.
[0012] Traditional additive manufacturing of aluminum alloys involves high alloy element content. During laser additive manufacturing, the high temperature gradient and fast solidification rate within the molten pool lead to high internal stress in the formed parts, making them prone to hot cracking defects and reducing mechanical properties. This invention employs nano-reinforcing agents with nano-effects, which are more easily and uniformly dispersed in the aluminum alloy matrix to form a dispersed reinforcing agent and act as a pinning agent. This effectively hinders the development of microcracks and promotes grain refinement, further enhancing the mechanical properties of the alloy.
[0013] In aluminum-magnesium alloys suitable for additive manufacturing, magnesium content is high. However, magnesium volatilizes during 3D printing, producing a large amount of black smoke and forming pores on the aluminum alloy surface, thus reducing the yield strength of the alloy. This invention uses zirconium to replace part of the magnesium. The addition of zirconium promotes the formation of Al3Zr precipitates, resulting in grain boundary pinning and acting as a non-uniform nucleation point in the aluminum alloy. This effectively reduces the grain size of the aluminum alloy, thereby reducing its susceptibility to cracking and improving its mechanical strength. Vanadium has a low diffusion rate in aluminum alloys, which can enhance the high-temperature strength of the alloy. Simultaneously, vanadium can form intermetallic compounds with aluminum through a eutectic reaction, refining the grains, increasing the recrystallization temperature, and improving mechanical properties.
[0014] Furthermore, the high-strength aluminum-based alloy material comprises, by mass percentage, the following components: 2.4% magnesium, 1.9% zirconium, 1.35% manganese, 1.1% copper, 0.4% vanadium, 0.9% nano-reinforcing agent, and the balance aluminum; wherein the nano-reinforcing agent is zirconium oxychloride nanopowder.
[0015] This invention also provides a method for preparing a nano-reinforcing agent, wherein the zirconium oxychloride nanopowder is prepared by a sol-gel method using ZrOCl2·8H2O and a precipitant. The preparation method is as follows: (1) ZrOCl2·8H2O aqueous solution and ammonia water are simultaneously added dropwise to the precipitant solution, stirred and reacted, and allowed to stand for aging to obtain Zr(OH)4 gel; (2) The Zr(OH)4 gel obtained in step (1) is filtered and washed to obtain Zr(OH)4 hydrogel; (3) Anhydrous ethanol is added to the Zr(OH)4 hydrogel obtained in step (2), stirred, filtered, dried, ground, and then subjected to nitrogen gas. Under the conditions, the temperature is raised to 400-450℃ for heat treatment, the heat treatment time is 3.8-4.3h, cooled, and ground to obtain nano-reinforcing agent; wherein, the concentration of the ZrOCl2·8H2O aqueous solution in step (1) is 0.1-0.2mol / L, the pH value of the ammonia water is 9-10, the dropping rate of the ZrOCl2·8H2O aqueous solution and the ammonia water is 2.8-3.2mL / min, the precipitant is an ammonia water aqueous solution with a mass percentage of 2.5%-3.0%, the stirring reaction time is 2-2.5h, and the static aging time is 8-10h.
[0016] The precipitant solution is a receiving liquid / reaction mother liquor with a certain concentration of ammonia water, and the synchronous addition of ammonia water is used to adjust the pH / precipitation rate.
[0017] In this invention, zirconia nanoparticles are prepared using a ZrOCl2·8H2O aqueous solution and a precipitant via a sol-gel method. The particle size and specific surface area of the zirconia nanoparticles are further controlled by adjusting the temperature and time of heat treatment. Studies have shown that excessively high heat treatment temperatures or prolonged treatment times result in larger particle sizes and smaller specific surface areas of the prepared zirconia nanoparticles. Furthermore, the addition of anhydrous ethanol to the hydrogel in this invention displaces the water, forming an alcohol gel. Heat treatment under flowing nitrogen effectively removes water from the gel, preventing hard agglomeration of the zirconia nanoparticles and facilitating the preparation of nanoscale zirconia nanoparticles.
[0018] Furthermore, the mass fractions of each component in the preparation method of the nano-reinforcing agent are as follows: 20-30 parts of ZrOCl2·8H2O aqueous solution, 10-16 parts of ammonia water, 10-15 parts of precipitant solution, and 8-12 parts of anhydrous ethanol.
[0019] Furthermore, the high-strength aluminum-based alloy material comprises, by mass percentage, the following components: 2.4% magnesium, 1.9% zirconium, 1.35% manganese, 1.1% copper, 0.4% vanadium, 0.9% nano-reinforcing agent, and the balance aluminum.
[0020] The present invention also provides a production process for the high-strength aluminum-based alloy material, comprising the following steps:
[0021] S1: Add each component of the high-strength aluminum-based alloy material formula into a melting furnace, evacuate the furnace, and heat and melt it under inert gas protection to obtain a metal melt;
[0022] S2: Vacuum atomize the molten metal using an inert gas as the atomizing medium to obtain a high-strength aluminum-based alloy material.
[0023] Furthermore, the inert gas in steps S1 and S2 is helium or argon, and the pressure of the inert gas in the melting furnace in step S1 is 2.4-3.0 MPa.
[0024] In this invention, the volatilization of elements in aluminum-based alloy materials is reduced by controlling the pressure in the melting furnace.
[0025] Furthermore, in step S1, the temperature is heated to 1250-1400°C to melt all the components.
[0026] Furthermore, the flow rate of the molten metal in step S2 is 10-15 g / s.
[0027] Compared with existing technologies, the high-strength aluminum-based alloy material and its production process provided by this invention have the following technical advantages:
[0028] (1) This invention effectively reduces the grain size of aluminum alloys and improves their mechanical strength by optimizing the formulation of aluminum-based alloy materials;
[0029] (2) In this invention, a nano-reinforcing agent is prepared by sol-gel method using ZrOCl2·8H2O aqueous solution and precipitant. It forms a dispersed reinforcing agent in aluminum-based alloy materials and plays a pinning role, effectively hindering the development of microcracks and promoting grain refinement, thereby further enhancing the mechanical properties of the alloy.
[0030] (3) The high-strength aluminum-based alloy material provided by the present invention has a tensile strength of not less than 625 MPa, a yield strength of not less than 597 MPa, an elongation of not less than 20%, and excellent comprehensive performance. Detailed Implementation
[0031] The present invention will be further described below with reference to specific embodiments, but the present invention is not limited to the following embodiments. Those skilled in the art can make various modifications based on the basic idea of the present invention, but as long as they do not depart from the basic idea of the present invention, they are all within the scope of the present invention.
[0032] The molded parts of each embodiment and comparative example were prepared using the same 3D printing process conditions; tensile property tests were conducted at room temperature, and the specific test methods were performed in accordance with the standard for room temperature tensile testing of metallic materials.
[0033] Example 1: A high-strength aluminum-based alloy material, comprising the following components by mass percentage:
[0034] Magnesium 1.0%, zirconium 2.7%, manganese 1.25%, copper 0.8%, vanadium 0.2%, nano-reinforcing agent 0.7%, and balance aluminum.
[0035] The specific preparation method of the nano-reinforcing agent is as follows: (1) 20g of ZrOCl2·8H2O aqueous solution with a concentration of 0.1mol / L and 10g of ammonia water with a pH value of 9 are simultaneously added dropwise to 10g of ammonia water aqueous solution with a mass percentage of 2.5% at a rate of 2.8mL / min. The mixture is stirred for 2h and allowed to stand for aging for 8h to obtain Zr(OH)4 gel; (2) The Zr(OH)4 gel obtained in step (1) is filtered and washed until there are no chloride ions in the washing liquid to obtain Zr(OH)4 hydrogel; (3) 8g of anhydrous ethanol is added to the Zr(OH)4 hydrogel obtained in step (2), stirred thoroughly for 2h, filtered, and the obtained filter cake is placed in a vacuum drying oven and dried at 100℃ for 24h. It is then taken out and ground into powder. Under the condition of nitrogen gas, the temperature is raised to 400℃ for heat treatment for 3.8h, cooled, and ground to obtain nano-reinforcing agent.
[0036] The production process of high-strength aluminum-based alloy materials includes the following steps:
[0037] S1: Add each component of the high-strength aluminum-based alloy material formula to the melting furnace, evacuate and introduce helium or argon gas to maintain the pressure in the melting furnace at 2.4 MPa, heat to 1250℃ to melt, and obtain a metal melt;
[0038] S2: The molten metal obtained in step S1 is vacuum atomized with an inert gas at a flow rate of 10 g / s to obtain a high-strength aluminum-based alloy material.
[0039] Example 2: A high-strength aluminum-based alloy material, comprising the following components by mass percentage:
[0040] Magnesium 3.2%, zirconium 1.0%, manganese 1.53%, copper 1.4%, vanadium 0.5%, nano-reinforcing agent 1.0%, and balance aluminum.
[0041] The specific preparation method of the nano-reinforcing agent is as follows: (1) 30g of ZrOCl2·8H2O aqueous solution with a concentration of 0.2mol / L and 16g of ammonia water with a pH value of 10 are simultaneously added dropwise to 15g of ammonia water aqueous solution with a mass percentage of 3.0% at a rate of 3.2mL / min. The mixture is stirred for 2.5h and allowed to stand for aging for 10h to obtain Zr(OH)4 gel; (2) The Zr(OH)4 gel obtained in step (1) is filtered and washed until there are no chloride ions in the washing liquid to obtain Zr(OH)4 hydrogel; (3) 12g of anhydrous ethanol is added to the Zr(OH)4 hydrogel obtained in step (2), stirred thoroughly for 2h, filtered, and the obtained filter cake is placed in a vacuum drying oven and dried at 100℃ for 24h. The cake is then taken out and ground into powder. Under the condition of nitrogen gas, the temperature is raised to 450℃ for heat treatment for 4.3h, cooled, and ground to obtain nano-reinforcing agent.
[0042] The production process of high-strength aluminum-based alloy materials includes the following steps:
[0043] S1: Add each component of the high-strength aluminum-based alloy material formula to the melting furnace, evacuate and introduce helium or argon gas to maintain the pressure in the melting furnace at 3.0 MPa, heat to 1400℃ to melt, and obtain the metal melt;
[0044] S2: The molten metal obtained in step S1 is vacuum atomized with an inert gas at a flow rate of 15 g / s to obtain a high-strength aluminum-based alloy material.
[0045] Example 3: A high-strength aluminum-based alloy material, comprising the following components by mass percentage:
[0046] Magnesium 2.4%, zirconium 1.9%, manganese 1.35%, copper 1.1%, vanadium 0.4%, nano-reinforcing agent 0.9%, and balance aluminum.
[0047] The specific preparation method of the nano-reinforcing agent is as follows: (1) 26g of ZrOCl2·8H2O aqueous solution with a concentration of 0.15mol / L and 13g of ammonia water with a pH of 9.5 are simultaneously added dropwise to 12g of ammonia water aqueous solution with a mass percentage of 2.8% at a rate of 3.0mL / min. The mixture is stirred for 2.2h and allowed to stand for aging for 9.2h to obtain Zr(OH)4 gel; (2) The Zr(OH)4 gel obtained in step (1) is filtered and washed until there are no chloride ions in the washing liquid to obtain Zr(OH)4 hydrogel; (3) 10g of anhydrous ethanol is added to the Zr(OH)4 hydrogel obtained in step (2), stirred thoroughly for 2h, filtered, and the obtained filter cake is placed in a vacuum drying oven and dried at 100℃ for 24h. The cake is then taken out and ground into powder. Under the condition of nitrogen gas, the temperature is raised to 430℃ for heat treatment for 4.0h, cooled, and ground to obtain nano-reinforcing agent.
[0048] The production process of high-strength aluminum-based alloy materials includes the following steps:
[0049] S1: Add each component of the high-strength aluminum-based alloy material formula to the melting furnace, evacuate and introduce helium or argon gas to maintain the pressure in the melting furnace at 2.8MPa, heat to 1310℃ to melt, and obtain the metal melt;
[0050] S2: The molten metal obtained in step S1 is vacuum atomized with an inert gas at a flow rate of 13 g / s to obtain a high-strength aluminum-based alloy material.
[0051] Comparative Example 1
[0052] The formulation and preparation method of the aluminum-based alloy material described in this comparative example are similar to those in Example 3. The difference between this comparative example and Example 3 is that an equal amount of magnesium is used instead of zirconium in this comparative example.
[0053] Comparative Example 2
[0054] The formulation and preparation method of the aluminum-based alloy material described in this comparative example are similar to those in Example 3. The difference between this comparative example and Example 3 is that an equal amount of aluminum is used to replace vanadium in this comparative example.
[0055] Comparative Example 3
[0056] The formulation and preparation method of the aluminum-based alloy material described in this comparative example are similar to those in Example 3. The difference between this comparative example and Example 3 is that an equal amount of aluminum is used to replace manganese in this comparative example.
[0057] Comparative Example 4
[0058] The formulation and preparation method of the aluminum-based alloy material described in this comparative example are similar to those in Example 3. The difference between this comparative example and Example 3 is that an equal amount of aluminum is used to replace the nano-reinforcing agent in this comparative example.
[0059] Comparative Example 5
[0060] The formulation and preparation method of the aluminum-based alloy material described in this comparative example are similar to those in Example 3. The difference between this comparative example and Example 3 is that the heat treatment temperature in the preparation method of the nano-reinforcing agent in this comparative example is 600℃ and the heat treatment time is 4.5h.
[0061] Comparative Example 6
[0062] The formulation and preparation method of the aluminum-based alloy material described in this comparative example are similar to those in Example 3. The difference between this comparative example and Example 3 is that an equal amount of deionized water is used instead of anhydrous ethanol in the preparation method of the nano-reinforcing agent in this comparative example.
[0063] Comparative Example 7
[0064] The formulation and preparation method of the aluminum-based alloy material described in this comparative example are similar to those in Example 3. The difference between this comparative example and Example 3 is that the pressure in the melting furnace is controlled to be 1.0 MPa in step S1 of the production process of the aluminum-based material in this comparative example.
[0065] Test case
[0066] In this experiment, 10×10cm aluminum alloy molded parts were prepared using aluminum-based alloy powders obtained in Examples 1-3 and Comparative Examples 1-7 via 3D printing technology. The yield strength, tensile strength, and elongation were tested according to GB / T 228-2002, "Metallic Materials - Tensile Testing at Room Temperature". The test results are shown in Table 1.
[0067] Table 1 Mechanical performance test results
[0068]
[0069] As shown in Table 1, the molded parts made using the high-strength aluminum-based alloy material provided by this invention have a tensile strength of not less than 625 MPa, a yield strength of not less than 597 MPa, and an elongation of not less than 20%, indicating that the high-strength aluminum-based alloy material provided by this invention has good mechanical properties. Among them, the aluminum-based alloy material obtained in Example 3 has the best performance in all aspects and is the best embodiment of this invention.
[0070] Compared to Example 3, Comparative Example 1 used an equal amount of magnesium instead of zirconium, but the yield strength of the resulting alloy material was significantly reduced. This was because the magnesium content was too high, causing it to volatilize during 3D printing and form pores on the surface of the aluminum-based alloy, resulting in a decrease in yield strength. Comparative Example 2 used an equal amount of aluminum instead of vanadium, but the mechanical properties of the resulting alloy material decreased to varying degrees, indicating that the addition of vanadium can improve the mechanical properties of aluminum-based alloy materials. Comparative Example 3 used an equal amount of aluminum instead of manganese, but the mechanical properties of the resulting alloy material decreased to varying degrees, indicating that the formulation of the present invention has been optimized. Comparative Example 4 used an equal amount of aluminum instead of nano-reinforcing agents, but the mechanical properties of the resulting alloy material deteriorated significantly. This indicates that the nano-reinforcing agents, when uniformly dispersed in the aluminum alloy matrix, can play a role in dispersion strengthening and pinning, effectively hindering the development of microcracks and improving the mechanical properties of the alloy. In Comparative Example 5, the preparation method of the nano-reinforcing agent changed the temperature and time of the heat treatment, but the... The mechanical properties of the resulting alloy materials decreased to varying degrees, indicating that the temperature and time of heat treatment are crucial for controlling the particle size of the nano-reinforcing agents during preparation. Excessive temperature or time results in larger nano-reinforcing agent particles, leading to uneven dispersion in the alloy material and affecting its mechanical properties. In Comparative Example 6, an equal amount of deionized water was used instead of anhydrous ethanol in the preparation of the nano-reinforcing agent, but the mechanical properties of the resulting alloy material decreased to varying degrees. This is because uneven or incomplete evaporation of water from the hydrogel during the preparation of the nano-reinforcing agent resulted in uneven particle size of the nano-reinforcing agent, weakening its dispersing effect in the alloy material and thus reducing its mechanical properties. In Comparative Example 7, the pressure in the melting furnace in step S1 of the aluminum-based material production process was changed, but the yield strength of the resulting alloy material decreased. This indicates that changing the pressure in the melting furnace causes magnesium in the raw materials to volatilize, forming pores on the surface of the alloy material, leading to a decrease in yield strength.
[0071] The above embodiments are merely illustrative of the preparation method of the present invention and are not intended to limit the invention. Those skilled in the art should not modify the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by those skilled in the art without departing from the technical concept provided by the present invention are still covered by the claims of the present invention.
Claims
1. A high-strength aluminum-based alloy material, characterized in that, By mass percentage, it includes the following components: Magnesium 1.0%-3.2%, zirconium 1.0%-2.7%, manganese 1.25%-1.53%, copper 0.8%-1.4%, vanadium 0.2%-0.5%, nano-reinforcing agent 0.7%-1.0%, and balance aluminum; the nano-reinforcing agent is zirconium oxychloride nanopowder.
2. The high-strength aluminum-based alloy material according to claim 1, characterized in that, The product comprises, by weight percentage, the following components: 2.4% magnesium, 1.9% zirconium, 1.35% manganese, 1.1% copper, 0.4% vanadium, 0.9% nano-reinforcing agent, and the balance aluminum; wherein the nano-reinforcing agent is zirconium oxychloride nanopowder.
3. A method for preparing a nano-reinforcing agent, characterized in that, The zirconium oxychloride nanopowder was prepared by a sol-gel method using ZrOCl2·8H2O and a precipitant. The preparation method is as follows: (1) Add ZrOCl2·8H2O aqueous solution and ammonia water dropwise to the precipitant solution, stir the reaction, let stand and age to obtain Zr(OH)4 gel; (2) The Zr(OH)4 gel obtained in step (1) is filtered and washed to obtain Zr(OH)4 hydrogel; (3) Add anhydrous ethanol to the Zr(OH)4 hydrogel obtained in step (2), stir, filter, dry, grind, and heat-treat at 400-450℃ under nitrogen gas for 3.8-4.3h, cool, grind, and obtain nano-reinforcing agent. In step (1), the concentration of the ZrOCl2·8H2O aqueous solution is 0.1-0.2 mol / L, the pH value of the ammonia water is 9-10, the dropping rate of the ZrOCl2·8H2O aqueous solution and the ammonia water is 2.8-3.2 mL / min, the precipitant is an ammonia water aqueous solution with a mass percentage of 2.5%-3.0%, the stirring reaction time is 2-2.5 h, and the standing aging time is 8-10 h.
4. The method for preparing the nano-reinforcing agent according to claim 3, characterized in that, The mass fractions of each component are: 20-30 parts of ZrOCl2·8H2O aqueous solution, 10-16 parts of ammonia water, 10-15 parts of precipitant solution, and 8-12 parts of anhydrous ethanol.
5. The production process of the high-strength aluminum-based alloy material according to any one of claims 1-2, characterized in that, Includes the following steps: S1: Add each component of the high-strength aluminum-based alloy material formula into a melting furnace, evacuate the furnace, and heat and melt it under inert gas protection to obtain a metal melt; S2: Vacuum atomize the molten metal using an inert gas as the atomizing medium to obtain a high-strength aluminum-based alloy material.
6. The production process of the high-strength aluminum-based alloy material according to claim 5, characterized in that, The inert gas in steps S1 and S2 is helium or argon, and the pressure of the inert gas in the melting furnace in step S1 is 2.4-3.0 MPa.
7. The production process of the high-strength aluminum-based alloy material according to claim 5, characterized in that, In step S1, the temperature is heated to 1250-1400℃ to melt all the components.
8. The production process of the high-strength aluminum-based alloy material according to claim 5, characterized in that, The flow rate of the molten metal in step S2 is 10-15 g / s.