Multi-nanophase reinforced aluminum-based composite material as well as preparation method and application thereof

Abstract

The invention provides a multi-nanophase reinforced aluminum-based composite material and a preparation method and application thereof, and belongs to the technical field of composite materials. The multi-nanophase reinforced aluminum-based composite material disclosed by the invention comprises a ZrB2 nano-particle reinforced phase, an Al2O3 nano-particle reinforced phase and an Al (Er, Y) 3 multi-nanophase. The Al (Er, Y) 3 multi-nanophase is obtained by adding double rare earth (Er, Y) for coupling and strengthening, the Al (Er, Y) 3 multi-nanophase cooperates with a ZrB2 nano-particle strengthening phase and an Al2O3 nano-particle strengthening phase, agglomeration of nano-particles is avoided, wettability of the nano-particles is improved, the nano-particles are uniformly dispersed, the high-toughness and anti-fatigue multi-nanophase strengthened aluminum-based composite material is obtained, and a high-precision thin-wall pipe can be prepared; meanwhile, double rare earth (Er, Y) is coupled and strengthened, so that the problems that single rare earth Er is high in price, low in solid solubility, large in quantity, easy to form coarse compounds and limited in performance improvement are solved.

Description

Technical Field

[0001] This invention relates to the field of composite materials technology, and in particular to a multi-nanophase reinforced aluminum-based composite material, its preparation method, and its application. Background Technology

[0002] In recent years, with the increasing scarcity of energy and the growing severity of environmental pollution, lightweighting, fatigue resistance, creep resistance, and long service life have become core requirements for various structural and functional components. Fields such as aerospace and rail transportation demand materials with higher modulus, specific strength, and specific stiffness, requiring excellent creep and fatigue resistance while meeting lightweighting requirements. Aluminum alloys, with their excellent casting properties, machinability, heat treatment toughening properties, and fatigue resistance, have become widely used high-performance aluminum alloys in automotive wheel hubs, engine blocks, shock absorber brackets, and oil pump housings.

[0003] Related records disclose the introduction of nano-dispersed phases into aluminum alloys to improve their strength and creep resistance. For example, this involves preparing A356.2-based composites reinforced with nano-ZrB2 particles, and adding rare earth Er to modify and refine the matrix, forming dispersed precipitated reinforcing phases to improve the composite's room-temperature mechanical properties and high-temperature creep resistance. Another example is the use of submicron particles to reinforce aluminum matrix composites for automotive wheel hubs, with the reinforcing particles being either Al2O3 submicron particles or a combination of Al2O3 and Al3Zr submicron particles, improving the wheel hub's dimensional stability. However, the aluminum matrix composites in these technologies still suffer from poor strength and toughness. Summary of the Invention

[0004] In view of this, the purpose of this invention is to provide a multi-nanophase reinforced aluminum-based composite material, its preparation method, and its application. The aluminum-based composite material provided by this invention has high strength and good toughness.

[0005] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0006] This invention provides a multi-nano phase reinforced aluminum matrix composite material, comprising the following phases: ZrB2 nanoparticle reinforcing phase, Al2O3 nanoparticle reinforcing phase, Al(Er,Y)3 multi-nano phase and aluminum matrix alloy phase;

[0007] The sum of the volume percentages of ZrB2 nanoparticles and Al2O3 nanoparticles in the multi-nano phase reinforced aluminum matrix composite material is 1-5%, the volume percentage ratio of ZrB2 nanoparticles to Al2O3 nanoparticles is 0.41-0.43:1, and the volume percentage of Al(Er,Y)3 multi-nano phase in the multi-nano phase reinforced aluminum matrix composite material is 0.5-0.6%.

[0008] Preferably, the sum of the volume percentages of the ZrB2 nanoparticle reinforcing phase and the Al2O3 nanoparticle reinforcing phase in the multi-nanophase reinforced aluminum matrix composite material is 3%.

[0009] Preferably, the particle size of the ZrB2 nanoparticle-reinforced phase is 80–100 nm.

[0010] Preferably, the particle size of the Al2O3 nanoparticle-reinforced phase is 80–100 nm.

[0011] This invention also provides a method for preparing the multi-nano phase reinforced aluminum matrix composite material described above, comprising the following steps:

[0012] K2ZrF6 and Na2B4O were mixed and ground to obtain powder;

[0013] The powder was mixed with pure aluminum and reacted in situ to obtain a (ZrB2+Al2O3) / Al nanoparticle composite melt.

[0014] After cooling, the (ZrB2+Al2O3) / Al nanoparticle composite melt is mixed with a matrix aluminum master alloy, an Al-Er rare earth alloy and an Al-Y rare earth alloy for coupling strengthening to obtain a multi-nano phase strengthened aluminum matrix composite melt.

[0015] The multi-nano phase reinforced aluminum matrix composite melt is sequentially subjected to casting, plastic forming, and heat treatment to obtain the multi-nano phase reinforced aluminum matrix composite material.

[0016] Preferably, the mass ratio of K2ZrF6 to Na2B4O is 0.41 to 0.43:1.

[0017] Preferably, the in-situ reaction is carried out at a temperature of 830–850°C for 25–30 minutes.

[0018] Preferably, the particle size of the powder is 200-250 mesh.

[0019] Preferably, the coupling enhancement temperature is 700–800°C and the time is 25–35 min.

[0020] The present invention also provides the application of the multi-nano phase reinforced aluminum matrix composite material described in the above technical solution or the multi-nano phase reinforced aluminum matrix composite material prepared by the preparation method described in the above technical solution in pipes.

[0021] This invention provides a multi-nano phase reinforced aluminum matrix composite material, comprising the following phases: ZrB2 nanoparticle reinforcing phase, Al2O3 nanoparticle reinforcing phase, Al(Er,Y)3 multi-nano phase and aluminum matrix alloy phase;

[0022] The sum of the volume percentages of ZrB2 nanoparticle reinforcing phase and Al2O3 nanoparticle reinforcing phase in the multi-nano phase reinforced aluminum matrix composite material is 1-5%, the volume percentage ratio of ZrB2 nanoparticle reinforcing phase to Al2O3 nanoparticle reinforcing phase is 0.41-0.43:1, and the volume percentage of Al(Er,Y)3 multi-nano phase in the multi-nano phase reinforced aluminum matrix composite material is 0.5-0.6%.

[0023] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0024] This invention achieves Al(Er,Y)3 multi-nano phases through the addition of dual rare earth (Er,Y) coupling reinforcement. These phases work synergistically with ZrB2 and Al2O3 nanoparticles to prevent nanoparticle aggregation, improve wettability and uniform dispersion, resulting in a high-strength, high-toughness, and fatigue-resistant multi-nano phase reinforced aluminum-based composite material. This material can be used to fabricate high-precision thin-walled tubing. Furthermore, the dual rare earth (Er,Y) coupling reinforcement avoids the problems of high price, low solid solubility, and the tendency for large quantities of Er to form coarse compounds with limited performance improvement, thus reducing costs and inhibiting the formation of coarse rare earth compound phases.

[0025] This invention also provides a method for preparing the multi-nano phase reinforced aluminum matrix composite material described in the above technical solution. Based on the Al-K2ZrF6-Na2B4O reaction system, this invention generates ZrB2 nanoparticle reinforcing phase, Al2O3 nanoparticle reinforcing phase, and Al(Er,Y)3 multi-nano phase by adding dual rare earth (Er,Y) coupling reinforcement effect, thereby obtaining a high-strength, high-toughness, and fatigue-resistant multi-nano phase reinforced aluminum matrix composite material, which can be used to prepare high-precision thin-walled tubes. Moreover, the preparation method of this invention is simple to operate and easy to realize industrial production. Attached Figure Description

[0026] Figure 1 EDS diagram of the 3 vol.% (ZrB2+Al2O3) / Al6061 high-precision thin-walled tube prepared in Comparative Example 1;

[0027] Figure 2 A schematic diagram of the process for preparing 3 vol.% (ZrB2+Al2O3)-0.4 vol.% Er-0.1 vol.% Y / Al6061 high-precision thin-walled tubing for Example 1;

[0028] Figure 3 SEM image of the 3 vol.% (ZrB2+Al2O3)-0.4 vol.% Er-0.1 vol.% Y / Al6061 high-precision thin-walled tube prepared in Example 1;

[0029] Figure 4This is a comparison graph of the tensile strength and elongation of Al6061, 3 vol.% (ZrB2+Al2O3) / Al6061 and 0.4Er-0.1Y / Al6061 prepared in Comparative Example 1, and 3 vol.% (ZrB2+Al2O3)-0.4 vol.%Er-0.1 vol.%Y / Al6061 prepared in Example 1;

[0030] Figures 5-7 The images show actual photos of the high-precision thin-walled tubes with different diameters of 0.5 mm, 1 mm, and 30 mm obtained in Examples 1-3 at different angles. Detailed Implementation

[0031] This invention provides a multi-nano phase reinforced aluminum matrix composite material, comprising the following phases: ZrB2 nanoparticle reinforcing phase, Al2O3 nanoparticle reinforcing phase, Al(Er,Y)3 multi-nano phase and aluminum matrix alloy phase;

[0032] The sum of the volume percentages of ZrB2 nanoparticle reinforcing phase and Al2O3 nanoparticle reinforcing phase in the multi-nano phase reinforced aluminum matrix composite material is 1-5%, the volume percentage ratio of ZrB2 nanoparticle reinforcing phase to Al2O3 nanoparticle reinforcing phase is 0.41-0.43:1, and the volume percentage of Al(Er,Y)3 multi-nano phase in the multi-nano phase reinforced aluminum matrix composite material is 0.5-0.6%.

[0033] In this invention, the sum of the volume percentages of ZrB2 nanoparticle reinforcing phase and Al2O3 nanoparticle reinforcing phase in the multi-nanophase reinforced aluminum matrix composite material can specifically be 1%, 2%, 3%, 4%, or 5%. The clusters of ZrB2 nanoparticle reinforcing phase and Al2O3 nanoparticle reinforcing phase will increase with the increase of the volume fraction of nanoparticles. Controlling the sum of the volume percentages of ZrB2 nanoparticle reinforcing phase and Al2O3 nanoparticle reinforcing phase within the above range can ensure that the multi-nanophase reinforced aluminum matrix composite material has excellent performance while the clusters are not obvious.

[0034] In this invention, the particle size of the ZrB2 nanoparticle-reinforced phase is preferably 80-100 nm, specifically 80, 90, or 100 nm; if the particle size of the ZrB2 nanoparticle-reinforced phase is too large or too small, it will lead to agglomeration and uneven particle dispersion.

[0035] In this invention, the particle size of the Al2O3 nanoparticle reinforcing phase is preferably 80-100 nm, specifically 80, 90, or 100 nm; if the particle size of the Al2O3 nanoparticle reinforcing phase is too large or too small, it will lead to agglomeration and uneven particle dispersion.

[0036] In this invention, the volume percentage of Al(Er,Y)3 multi-nano phase in the multi-nano phase reinforced aluminum matrix composite material can specifically be 0.5% or 0.6%.

[0037] In this invention, the multi-nano phase reinforced aluminum matrix composite material further includes a balance of aluminum matrix alloy phase, which is preferably a 6000 series aluminum alloy matrix phase or a 7000 series aluminum alloy matrix phase, more preferably a 6061 aluminum alloy matrix phase or a 7075 aluminum alloy matrix phase.

[0038] This invention obtains Al(Er,Y)3 multi-nano phase by adding dual rare earth (Er,Y) coupling reinforcement, which works synergistically with ZrB2 nanoparticle reinforcement phase and Al2O3 nanoparticle reinforcement phase to avoid nanoparticle agglomeration, improve nanoparticle wettability and uniform dispersion, and obtain a high-strength, high-toughness, fatigue-resistant multi-nano phase reinforced aluminum matrix composite material.

[0039] This invention also provides a method for preparing the multi-nano phase reinforced aluminum matrix composite material described above, comprising the following steps:

[0040] K2ZrF6 and Na2B4O were mixed and ground to obtain powder;

[0041] The powder was mixed with pure aluminum and reacted in situ to obtain a (ZrB2+Al2O3) / Al nanoparticle composite melt.

[0042] After cooling, the (ZrB2+Al2O3) / Al nanoparticle composite melt is mixed with a matrix aluminum master alloy, an Al-Er rare earth alloy and an Al-Y rare earth alloy for coupling strengthening to obtain a multi-nano phase strengthened aluminum matrix composite melt.

[0043] The multi-nano phase reinforced aluminum matrix composite melt is sequentially subjected to casting, plastic forming, and heat treatment to obtain the multi-nano phase reinforced aluminum matrix composite material.

[0044] Unless otherwise specified, all raw materials used in this invention are commercially available products in the field.

[0045] The present invention mixes and grinds K2ZrF6 and Na2B4O to obtain powder, preferably by mixing and grinding the K2ZrF6 and Na2B4O to obtain powder.

[0046] In this invention, the particle size of the powder is preferably 200-250 mesh, specifically 200, 210, 220, 230, 240 or 250 mesh.

[0047] In this invention, K2ZrF6 and Na2B4O are preferably pretreated separately before mixing. The pretreatment preferably includes sequential drying and removal of water of crystallization. This invention does not impose specific limitations on the parameters of the pretreatment; methods well-known to those skilled in the art can be used. In a specific embodiment of this invention, the drying temperature for both K2ZrF6 and Na2B4O is 180°C, and the drying time is 2 hours.

[0048] In this invention, the mass ratio of K2ZrF6 to Na2B4O is preferably 0.41 to 0.43:1, specifically 0.41:1, 0.42:1 or 0.43:1. Controlling the mass ratio of K2ZrF6 to Na2B4O within this range enables the formation of ZrB2 and Al2O3.

[0049] After the grinding is completed, the present invention preferably divides the obtained material into portions using aluminum foil for subsequent reactions. The portioning is preferably done by weight, and the number of portions is preferably 5 to 7, with each portion not exceeding 70g.

[0050] After obtaining the powder, the present invention mixes the powder with pure aluminum and carries out an in-situ reaction to obtain a (ZrB2+Al2O3) / Al nanoparticle composite melt.

[0051] In this invention, the temperature of the in-situ reaction is preferably 830-850°C, specifically 830, 840 or 850°C, and the time is preferably 25-30 min, specifically 25, 26, 27, 28, 29 or 30 min.

[0052] In this invention, the mass ratio of the powder to pure aluminum is preferably 0.23 to 0.24:1, specifically 0.23:1 or 0.24:1.

[0053] In this invention, the pure aluminum is preferably placed in a preheated graphite crucible and heated to 850°C using a medium-frequency induction heating furnace to obtain an aluminum melt. The powder obtained from the sub-package is added to the aluminum melt in several batches (preferably 3 to 5 times) while applying electromagnetic stirring. The stirring vortex is used to make the powder uniformly enter the aluminum melt. The temperature of the medium-frequency induction heating furnace is maintained to carry out the in-situ reaction. After the in-situ reaction is completed, a purification treatment is preferably performed to obtain a (ZrB2+Al2O3) / Al nanoparticle composite melt.

[0054] In this invention, the temperature of the preheated graphite crucible is preferably 830-850°C, specifically 830, 840 or 850°C, and the holding time is preferably 30-45 minutes, specifically 30 or 45 minutes.

[0055] In this invention, in order to prevent the powder from being deposited at the bottom of the graphite crucible due to electromagnetic stirring and thus causing insufficient reaction, it is preferable to turn off the electromagnetic stirring after 5 to 8 minutes, and then manually stir with a graphite rod and spoon for 2 to 3 minutes. When the white powder is observed to turn into black powder, the in-situ reaction is completely finished.

[0056] In this invention, the electromagnetic field current of the electromagnetic stirring is preferably 100A, and the frequency is 10 to 12Hz, specifically 10, 11 or 12Hz.

[0057] In this invention, the purification process preferably includes sequential slag removal, refining, and degassing. This invention does not impose any special limitations on the specific parameters of the purification process, and methods well known to those skilled in the art can be used.

[0058] In this invention, it is preferable to perform secondary slag removal after each addition of powder and reaction to ensure that the melt is pure when adding powder next time.

[0059] After obtaining the (ZrB2+Al2O3) / Al nanoparticle composite melt, the present invention cools the (ZrB2+Al2O3) / Al nanoparticle composite melt and mixes it with a matrix aluminum master alloy, an Al-Er rare earth alloy and an Al-Y rare earth alloy for coupling strengthening, thereby obtaining a multi-nano phase strengthened aluminum matrix composite melt.

[0060] In this invention, the Al-Er rare earth alloy is preferably Al-20Er.

[0061] In this invention, the Al-Y rare earth alloy is preferably Al-20Y.

[0062] In this invention, the base aluminum master alloy preferably includes pure magnesium, pure copper, pure zinc, aluminum-silicon alloy, aluminum-manganese alloy, and aluminum-chromium alloy.

[0063] In this invention, the aluminum-silicon alloy is preferably Al-20Si; the aluminum-manganese alloy is preferably Al-80Mn or Al-20Mn; and the aluminum-chromium alloy is preferably Al-20Cr.

[0064] In specific embodiments of the present invention, the base aluminum master alloy can be selected according to its application: for the research of high-strength and high-toughness precision tubing in aerospace, the base aluminum master alloy is selected from 6000 series aluminum alloys, more preferably 6061 aluminum alloy; for the research of high strength and high toughness in transportation, national defense and military fields, the base aluminum master alloy is selected from 7000 series aluminum alloys, more preferably 7075 aluminum alloy.

[0065] Preferably, the medium-frequency induction heating furnace is cooled to 750°C, and the base aluminum alloy (excluding pure magnesium), Al-Er rare earth alloy, and Al-Y rare earth alloy are added. Electromagnetic stirring is applied, and the stirring vortex is used to uniformly distribute the reaction alloys in the (ZrB2+Al2O3) / Al nanoparticle composite melt. The first reaction is carried out at 750–800°C (specifically 750, 760, 770, 780, 790, or 800°C) for 15–20 minutes (specifically 1 minute). After 5, 16, 17, 18, 19 or 20 min, the first melt is obtained. After the first melt is cooled to 700-720℃ (specifically 700, 710 or 720℃), pure magnesium is added. The second reaction is carried out at 700-720℃ (specifically 700, 710 or 720℃) for 10-15 min (specifically 10, 11, 12, 13, 14 or 15 min). After the reaction is completed, the melt is purified to obtain the multi-nano phase reinforced aluminum-based composite melt.

[0066] In this invention, the first melt preferably comprises the following elements in mass percentage: Al: 96.5-97%, Si: 0.7-0.75% (specifically 0.7, 0.71, 0.72, 0.73, 0.74, or 0.75%), Cu: 0.25-0.27% (specifically 0.25, 0.26, or 0.27%), Mn: 0.15-0.2% (specifically 0.25, 0.26, or 0.27%). 0.15, 0.16, 0.17, 0.18, 0.19 or 0.2%), Cr: 0.2%, Zn: 0.25-0.27% (specifically 0.25, 0.26 or 0.27%), Er: 0.3-0.7% (specifically 0.3, 0.4, 0.5, 0.6 or 0.7%), Y: 0.1-0.3% (specifically 0.1, 0.2 or 0.3%).

[0067] In this invention, the total mass percentage of the Al-Er rare earth alloy and the Al-Y rare earth alloy preferably does not exceed 0.5% of the total raw materials, and more preferably is less than 0.4%, to avoid the formation of coarse intermetallic compounds due to excessive rare earth.

[0068] In this invention, the mass ratio of pure magnesium to the first melt is preferably 0.8 to 1:1, specifically 0.8:1, 0.9:1 or 1:1.

[0069] After adding the pure magnesium, in order to prevent the pure magnesium from emitting a bright white light upon contact with air, it is preferable to press the pure magnesium into the bottom of the graphite crucible with a graphite rod and react for 1 to 2 minutes, and then turn on the electromagnetic stirring to ensure that the reaction is complete.

[0070] In this invention, the temperature for the coupling enhancement is preferably 700-800°C, and the time is preferably 25-35 min. The coupling enhancement includes a first reaction and a second reaction.

[0071] After obtaining the multi-nano phase reinforced aluminum-based composite melt, the present invention sequentially performs casting, plastic forming and heat treatment on the multi-nano phase reinforced aluminum-based composite melt to obtain the multi-nano phase reinforced aluminum-based composite material.

[0072] In this invention, the multi-nano phase reinforced aluminum-based composite melt is heated from the temperature of the second reaction to 750-800°C within 5-10 minutes before being cast to obtain a casting.

[0073] In this invention, the casting process is preferably carried out in a preheated pure copper mold. The temperature of the preheated pure copper mold is preferably 250–300°C, specifically 250, 260, 270, 280, 290, or 300°C, and the holding time is preferably 2–3 hours, specifically 2 or 3 hours. This invention does not impose any special limitations on the specific parameters of the casting process; methods well known to those skilled in the art can be used.

[0074] After obtaining the casting, the present invention performs plastic forming on the casting to obtain composite material pipe.

[0075] In this invention, the casting process is preferably performed sequentially by integral piercing reverse extrusion, composite rolling, and floating drawing.

[0076] In this invention, the integrated perforated reverse extrusion can improve the wall thickness accuracy and inner and outer surface quality of the composite material pipe. The extrusion outlet temperature of the integrated perforated reverse extrusion is preferably 550-568℃, specifically 550, 560, 565 or 568℃. The endpoint of the integrated perforated reverse extrusion is preferably the average grain size difference of the resulting solid is less than 5μm.

[0077] In this invention, the composite rolling and floating drawing processes are used to significantly improve the dimensional accuracy and surface quality of thin-walled tubes. This invention does not impose specific limitations on the parameters of the composite rolling and floating drawing processes. The preferred endpoints of the composite rolling and floating drawing processes include: aluminum alloy tubes with a wall thickness tolerance of -2% to +5% and an outer diameter tolerance of 0 to +0.08 mm (6 to 25 mm) and 0 to +0.12 mm (26 to 40 mm); and a 90° bend surface without orange peel texture and a surface grain size ≤ grade 1.

[0078] In this invention, the heat treatment (solution aging treatment) is preferably defined according to the application of the base aluminum master alloy. When the base aluminum master alloy is a 6000 series aluminum alloy, the solution aging treatment is preferably performed according to T6, specifically: holding at 545-550℃ (specifically 545, 546, 547, 548, 549, or 550℃) for 2-3 hours (specifically 2 or 3 hours), quenching, and holding at 175-180℃ (specifically 175, 176, 177, 178, 179, or 180℃) for 6-12 hours (specifically 6, 7, or 180℃). After 8, 9, 10, 11 or 12 hours, the solution aging treatment is cooled in the furnace. When the base aluminum master alloy is a 7000 series aluminum alloy, the solution aging treatment is preferably carried out according to T6, specifically: holding at 470-500℃ (specifically 470, 480, 490 or 500℃) for 2-3 hours (specifically 2 or 3 hours), quenching, holding at 120-180℃ (specifically 120, 130, 140, 150, 160, 170 or 180℃) for 12-24 hours (specifically 12, 14, 16, 18, 20, 22 or 24 hours), and then cooling in the furnace.

[0079] This invention also provides the application of the multi-nano phase reinforced aluminum matrix composite material described in the above technical solution or the multi-nano phase reinforced aluminum matrix composite material prepared by the above technical solution in the field of pipe materials.

[0080] The technical solutions of this invention will be clearly and completely described below with reference to the embodiments thereof. Obviously, the described embodiments are only a part of the embodiments of this invention, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0081] Comparative Example 1

[0082] First, K2ZrF6 powder and Na2B4O powder were dried (drying temperature 180℃, time 2h) and pretreated to remove crystal water. Then, based on the 3 vol.% (ZrB2+Al2O3) nanoparticle content generated in situ, the pretreated Na2B4O (113.84g) and K2ZrF6 (273.22g) powders were mixed and ground to 200 mesh. They were then packaged in aluminum foil and divided into 5 equal parts by mass. Pure aluminum (1652.11g) was placed in a preheated graphite crucible (850℃). The temperature was raised to 850℃ using a medium-frequency induction heating furnace. The pre-packaged reaction powder was added to the molten aluminum in five portions, one portion at a time, while applying electromagnetic stirring (100A electromagnetic field current, 10Hz frequency). After the reaction powder was evenly dispersed into the melt, the furnace was kept at 850℃ for 30 minutes. Then, slag removal, refining, and degassing were performed. This process was repeated after each addition of reaction powder. Slag was removed to ensure the purity of the melt for the next addition of reaction powder. The furnace was cooled to 750°C, and Al-20Si (62.02g), Cu (4.43g), Al-20Mn (26.58g), Al-20Cr (4.73g), and Zn (4.43g) were added. Magnetic stirring was applied (magnetic field current 100A, frequency 10Hz). After reacting for 20 minutes, the temperature was lowered to 700°C, and pure Mg (17.72g) was added. The reaction was continued at 700°C. The process should last 10 minutes, followed by purification. Once the melt temperature reaches 750℃, it is poured into a preheated pure copper mold (250℃, held for 2 hours). Integrated piercing reverse extrusion (extrusion outlet temperature 550℃, average grain size difference less than 5μm) + composite rolling and floating drawing technology is then applied to achieve aluminum alloy tube products with a wall thickness tolerance of -2% to +5%, an outer diameter tolerance of 0.1mm (30mm diameter), no orange peel on the 90° bend surface, and a surface grain size ≤ grade 1. The resulting sample is then heat-treated: held at 545℃ for 2 hours, quenched, held at 175℃ for 6 hours, and then cooled in the furnace. This yields a 3 vol.% (ZrB2+Al2O3) / Al6061 high-precision thin-walled tube with a tensile strength of 339MPa and an elongation of 11.3%, representing increases of 16.5% and 21.5% respectively compared to the 6061 aluminum alloy matrix.

[0083] Figure 1 The EDS diagram of the 3 vol.% (ZrB2+Al2O3) / Al6061 high-precision thin-walled tube prepared in Comparative Example 1 shows that ZrB2 and Al2O3 nanoparticles were successfully prepared in the 6061 aluminum alloy matrix.

[0084] Comparative Example 2

[0085] Pure aluminum (1596.46g) was placed in a preheated graphite crucible (850℃). The temperature was raised to 850℃ using a medium-frequency induction furnace, and electromagnetic stirring was applied (electromagnetic field current 100A, frequency 10Hz). The furnace was maintained at 850℃ for 30 minutes. Slag removal, refining, and degassing were then performed. A second slag removal was required after each addition of reaction powder to ensure the purity of the melt for the next addition. The furnace was then cooled to 750℃, and Al-20Si (62.156g), Cu (4.44g), Al-80Mn (3.33g), Al-20Cr (4.74g), Zn (4.44g), and Al-20Er (53g) were added. 0.28g) was added, and electromagnetic stirring was applied (electromagnetic field current was 100A, frequency was 10Hz). After reacting for 20min, the temperature was lowered to 700℃ and pure Mg (17.76g) was added. The reaction was carried out at 700℃ for 10min, and then purified. When the melt temperature was raised to 750℃, it was poured into a preheated pure copper mold (250℃, held for 2h). Then the obtained sample was heat-treated as follows: held at 545℃ for 2h, quenched, held at 175℃ for 6h and then cooled with the furnace. Finally, 0.4 vol.% Er / Al6061 high-precision thin-walled tube was obtained with a tensile strength of 343MPa and an elongation of 11.07%, which were 17.9% and 19% higher than those of 6061 aluminum matrix, respectively.

[0086] Comparative Example 3

[0087] Pure aluminum (1334.79g) was placed in a preheated graphite crucible (850℃), and heated to 850℃ using a medium-frequency induction furnace. Electromagnetic stirring was applied (electromagnetic field current 100A, frequency 10Hz), and the furnace was maintained at 850℃ for 30 minutes. Then, slag removal, refining, and degassing were performed. A second slag removal was required after each addition of reaction powder to ensure the purity of the melt for the next addition. The furnace was then cooled to 750℃, and Al-20Si (49.94g), Cu (3.57g), Al-80Mn (2.66g), Al-20Cr (3.8g), Zn (3.57g), and Al-20Y (14.2g) were added. 7g), electromagnetic stirring was applied (electromagnetic field current of 100A, frequency of 10Hz), and after reacting for 20min, the temperature was lowered to 700℃ and pure Mg (14.27g) was added. The reaction was carried out at 700℃ for 10min, and then purified. When the melt temperature was raised to 750℃, it was poured into a preheated pure copper mold (250℃, held for 2h). Then the obtained sample was heat-treated as follows: held at 545℃ for 2h, quenched, held at 175℃ for 6h and then cooled with the furnace. Finally, 0.1 vol.% Y / Al6061 high-precision thin-walled tube was obtained with a tensile strength of 330MPa and an elongation of 13.4832%, which were 13.4% and 45% higher than those of 6061 aluminum matrix, respectively.

[0088] Comparative Example 4

[0089] First, K2ZrF6 powder and Na2B4O powder were dried (drying temperature 180℃, time 2h) and pretreated to remove crystal water. Then, based on the 3 vol.% (ZrB2+Al2O3) nanoparticle content generated in situ, the pretreated Na2B4O (105.64g) and K2ZrF6 (253.53g) powders were mixed and ground to 200 mesh. They were then packaged in aluminum foil and divided into 5 equal parts by mass. Pure aluminum (1508) was also prepared. 38g) was placed in a preheated graphite crucible (850℃). The temperature was raised to 850℃ using a medium-frequency induction heating furnace. The pre-packaged reaction powder was added to the aluminum melt in five portions, one portion at a time. Electromagnetic stirring was applied (electromagnetic field current of 100A, frequency of 10Hz). After the reaction powder was evenly dispersed into the melt, the furnace was kept at 850℃ for 30 minutes. Then, slag removal, refining, and degassing were performed. Slag removal was performed twice after each addition of reaction powder to ensure that the melt was pure for the next addition of reaction powder. The furnace was cooled to 750℃, and Al-20Si (57.55g), Cu (4.11g), Al-20Mn (24.66g), Al-20Cr (4.38g), Zn (4.11g), and Al-20Er (24.66g) were added. Magnetic stirring was applied (electromagnetic field current of 100A and frequency of 10Hz). After reacting for 20 minutes, the temperature was lowered to 700℃, and pure Mg (16.44g) was added. The reaction was carried out at 700℃ for 10 minutes, and then purified. When the melt temperature reaches 750℃, it is poured into a preheated pure copper mold (250℃, held for 2 hours). The resulting sample is then heat-treated as follows: held at 545℃ for 2 hours, quenched, held at 175℃ for 6 hours, and then cooled in the furnace. Finally, a 3 vol.% (ZrB2+Al2O3)-0.4 vol.% Er / Al6061 high-precision thin-walled tube is obtained, with a tensile strength of 355 MPa and an elongation of 12.3%, which are 22.3% and 32.3% higher than those of the 6061 aluminum alloy matrix, respectively.

[0090] Comparative Example 5

[0091] First, K2ZrF6 powder and Na2B4O powder were dried (drying temperature 180℃, time 2h) and pretreated to remove crystal water. Then, based on the 3 vol.% (ZrB2+Al2O3) nanoparticle content generated in situ, the pretreated Na2B4O (103.34g) and K2ZrF6 (248.02g) powders were mixed and ground to 200 mesh. They were then packaged in aluminum foil and divided into 5 equal parts by mass. Pure aluminum (1491...) 0.69g) was placed in a preheated graphite crucible (850℃). The temperature was raised to 850℃ using a medium-frequency induction heating furnace. The pre-packaged reaction powder was added to the aluminum melt in five portions, one portion at a time, while applying electromagnetic stirring (electromagnetic field current of 100A and frequency of 10Hz). After the reaction powder was evenly dispersed into the melt, the furnace was kept at 850℃ for 30 minutes. Then, slag removal, refining, and degassing were performed. A second slag removal was required after each addition of reaction powder to ensure the purity of the melt for the next addition of reaction powder. Clean; cool the furnace to 750℃, add Al-20Si (56.3g), Cu (4.02g), Al-20Mn (24.13g), Al-20Cr (4.29g), Zn (4.02g), and Al-20Y (8.04g), apply electromagnetic stirring (electromagnetic field current of 100A, frequency of 10Hz), react for 20min, cool to 700℃ and add pure Mg (16.09g), react at 700℃ for 10min, and then purify. When the melt temperature reaches 750℃, it is poured into a preheated pure copper mold (250℃, held for 2 hours). The resulting sample is then heat-treated as follows: held at 545℃ for 2 hours, quenched, held at 175℃ for 6 hours, and then cooled in the furnace. Finally, 3 vol.% (ZrB2+Al2O3)-0.1 vol.% Y / Al6061 high-precision thin-walled tubing is obtained, with a tensile strength of 349 MPa and an elongation of 14.2%, which are 19.9% ​​and 52.7% higher than those of the 6061 aluminum alloy matrix, respectively.

[0092] Example 1

[0093] First, K2ZrF6 powder and Na2B4O powder were dried (drying temperature 180℃, time 2h) and pretreated to remove crystal water. Then, based on the 3 vol.% (ZrB2+Al2O3) nanoparticle content generated in situ, the pretreated Na2B4O (117.82g) and K2ZrF6 (282.77g) powders were mixed and ground to 200 mesh. They were then packaged in aluminum foil and divided into 5 equal parts by mass. Pure aluminum (16 88.05g of the reaction powder was placed in a preheated graphite crucible (850℃). The temperature was raised to 850℃ using a medium-frequency induction heating furnace. The pre-packaged reaction powder was added to the molten aluminum in five portions, one portion at a time, while applying electromagnetic stirring (electromagnetic field current of 100A and frequency of 10Hz). After the reaction powder was evenly dispersed into the melt, the furnace was kept at 850℃ for 30 minutes. Then, slag removal, refining, and degassing were performed. A second slag removal was required after each addition of reaction powder to ensure the next addition of reaction powder. The melt was pure. The furnace was cooled to 750℃, and Al-20Si (64.19g), Cu (4.59g), Al-80Mn (3.44g), Al-20Cr (4.9g), Zn (4.59g), Al-20Er (36.68g), and Al-20Y (9.17g) were added. Magnetic stirring was applied (electromagnetic field current 100A, frequency 10Hz). After reacting for 20 minutes, the temperature was lowered to 700℃ and pure Mg (18.34g) was added. The reaction is carried out at 700℃ for 10 minutes, followed by purification. When the melt temperature rises to 750℃, it is poured into a preheated pure copper mold (250℃, held for 2 hours). Integrated piercing reverse extrusion (extrusion outlet temperature is 550℃, average grain size difference is less than 5μm) + composite rolling and floating drawing technology are used to achieve aluminum alloy tube products with a wall thickness tolerance of -2% to +5%, an outer diameter tolerance of 0.1mm (pipe diameter 30mm), no orange peel on the surface of the 90° bend of the guide tube, and a surface grain size ≤ grade 1. The obtained sample was then subjected to heat treatment, which involved holding at 545℃ for 2 hours, quenching, holding at 175℃ for 6 hours, and then cooling in the furnace. The final product was a 3 vol.% (ZrB2+Al2O3)-0.4 vol.% Er-0.1 vol.% Y / Al6061 high-precision thin-walled tube with a tensile strength of 378 MPa and an elongation of 16.686%, which were 29.8% and 79% higher than those of the 6061 aluminum matrix, respectively.

[0094] Comparative Example 6

[0095] Similar to Example 1, except that K2ZrF6 powder and Na2B4O powder were not added to prepare 0.4 vol.% Er-0.1 vol.% Y / Al6061 (0.4 Er-0.1 Y / Al6061) thin-walled tubing.

[0096] Figure 2 A schematic diagram of the process for preparing 3 vol.% (ZrB2+Al2O3)-0.4 vol.% Er-0.1 vol.% Y / Al6061 high-precision thin-walled tubing for Example 1.

[0097] Figure 3 The image shows a SEM image of the 3 vol.% (ZrB2+Al2O3)-0.4 vol.% Er-0.1 vol.% Y / Al6061 high-precision thin-walled tube prepared in Example 1. The image shows that the coupling effect between the in-situ ZrB2 nanoparticle reinforcing phase, the Al2O3 nanoparticle reinforcing phase, and Y and Er produces a stronger grain refinement effect, and the grain structure of the composite material is further refined. In addition, a large number of needle-like iron-rich phases in the 6061 matrix alloy are transformed into skeletal iron-rich phases, which improves the strength, toughness and fatigue resistance of the aluminum-based composite material.

[0098] Figure 4 This is a comparison graph of the tensile strength and elongation of Al6061, 3 vol.% (ZrB2+Al2O3) / Al6061 and 0.4Er-0.1Y / Al6061 prepared in Comparative Example 1, and 3 vol.% (ZrB2+Al2O3)-0.4 vol.%Er-0.1 vol.%Y / Al6061 prepared in Example 1. As can be seen from the graph, the tensile strength and elongation of the prepared composite materials are improved under the reinforcement of nanoparticles and the coupling reinforcement of the two rare earth elements (Er, Y).

[0099] Example 2

[0100] First, K2ZrF6 powder and Na2B4O powder were dried (drying temperature 180℃, time 2h) and pretreated to remove crystal water. Then, based on the 3 vol.% (ZrB2+Al2O3) nanoparticle content generated in situ, the pretreated Na2B4O (116.62g) and K2ZrF6 (279.89g) powders were mixed and ground to 200 mesh. They were then packaged in aluminum foil and divided into 5 equal parts by mass. Pure aluminum (16 70.88g of the reaction powder was placed in a preheated graphite crucible (850℃). The temperature was raised to 850℃ using a medium-frequency induction heating furnace. The pre-packaged reaction powder was added to the molten aluminum in five portions, one portion at a time, while applying electromagnetic stirring (electromagnetic field current of 100A and frequency of 10Hz). After the reaction powder was evenly dispersed into the melt, the furnace was kept at 850℃ for 30 minutes. Then, slag removal, refining, and degassing were performed. A second slag removal was required after each addition of reaction powder to ensure the next addition of reaction powder. The melt was pure. The furnace was cooled to 750℃, and Al-20Si (63.53g), Cu (4.54g), Al-80Mn (3.4g), Al-20Cr (4.84g), Zn (4.54g), Al-20Er (27.23g), and Al-20Y (18.15g) were added. Magnetic stirring was applied (electromagnetic field current 100A, frequency 10Hz). After reacting for 20 minutes, the temperature was lowered to 700℃ and pure Mg (18.15g) was added. The mixture is reacted at 700℃ for 10 minutes, followed by purification. The melt temperature is then raised to 750℃ and poured into a preheated pure copper mold (250℃, held for 2 hours). Integrated perforated reverse extrusion (extrusion outlet temperature 550℃, average grain size difference less than 5μm) + composite rolling and floating drawing technology are then applied to achieve aluminum alloy tube products with a wall thickness tolerance of -2% to +5%, an outer diameter of 1mm with a tolerance of 0.05mm, no orange peel on the 90° bend surface, and a surface grain size ≤ grade 1. The obtained sample was then subjected to heat treatment, which involved holding at 545℃ for 2 hours, quenching, holding at 175℃ for 6 hours, and then cooling in the furnace. The final product was a 3 vol.% (ZrB2+Al2O3)-0.333 vol.% Er-0.233 vol.% Y / Al6061 high-precision thin-walled tube with a tensile strength of 370 MPa and an elongation of 16%, which were 27.1% and 72.04% higher than those of the 6061 aluminum matrix, respectively.

[0101] Example 3

[0102] First, K2ZrF6 powder and Na2B4O powder were dried (drying temperature 180℃, time 2h) and pretreated to remove crystal water. Then, based on the 3 vol.% (ZrB2+Al2O3) nanoparticle content generated in situ, the pretreated Na2B4O (116.62g) and K2ZrF6 (279.89g) powders were mixed and ground to 200 mesh. They were then packaged in aluminum foil and divided into 5 equal parts by mass. Pure aluminum (1 713.86g of the reaction powder was placed in a preheated graphite crucible (850℃). The temperature was raised to 850℃ using a medium-frequency induction heating furnace. The pre-packaged reaction powder was added to the molten aluminum in five portions, one portion at a time, while applying electromagnetic stirring (electromagnetic field current of 100A and frequency of 10Hz). After the reaction powder was evenly dispersed into the melt, the furnace was kept at 850℃ for 30 minutes. Then, slag removal, refining, and degassing were performed. A second slag removal was required after each addition of reaction powder to ensure the next addition of reaction powder. Finally, the melt was pure. The furnace was cooled to 750℃, and Al-20Si (65.17g), Cu (4.7g), Al-80Mn (3.5g), Al-20Cr (5g), Zn (4.7g), Al-20Er (27.93g), and Al-20Y (18.62g) were added. Magnetic stirring was applied (electromagnetic field current 100A, frequency 10Hz). After reacting for 20 minutes, the temperature was lowered to 700℃, and pure Mg (18.62g) was added. The reaction is carried out at 700℃ for 10 minutes, followed by purification. When the melt temperature rises to 750℃, it is poured into a preheated pure copper mold (250℃, held for 2 hours). The process involves integrated piercing reverse extrusion (extrusion outlet temperature is 550℃, average grain size difference is less than 5μm) + composite rolling and floating drawing technology to achieve aluminum alloy tube products with a wall thickness tolerance of -2% to +5%, an outer diameter of 0.5mm with a tolerance of 0.03mm, no orange peel on the surface of the 90° bend of the conduit, and a surface grain size ≤ grade 1. The obtained sample was then subjected to heat treatment, which involved holding at 545℃ for 2 hours, quenching, holding at 175℃ for 6 hours, and then cooling in the furnace. The final product was a 3 vol.% (ZrB2+Al2O3)-0.3 vol.% Er-0.2 vol.% Y / Al6061 high-precision thin-walled tube with a tensile strength of 368 MPa and an elongation of 16.3%, which were 26.6% and 75.3% higher than those of the 6061 aluminum matrix, respectively.

[0103] Figures 5-7 The images show actual photos of the high-precision thin-walled tubes with different diameters of 0.5 mm, 1 mm, and 30 mm obtained in Examples 1-3 at different angles.

[0104] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. It should be noted that those skilled in the art can make various improvements and modifications without departing from the principles of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A multi-nanophase reinforced aluminum-based composite material, characterized in that, It includes the following phase composition: ZrB2 nanoparticle reinforced phase, Al2O3 nanoparticle reinforced phase, Al(Er,Y)3 multi-nano phase and aluminum matrix alloy phase; The sum of the volume percentages of ZrB2 nanoparticle reinforcing phase and Al2O3 nanoparticle reinforcing phase in the multi-nano phase reinforced aluminum matrix composite material is 1-5%, the volume percentage ratio of ZrB2 nanoparticle reinforcing phase to Al2O3 nanoparticle reinforcing phase is 0.41-0.43:1, and the volume percentage of Al(Er,Y)3 multi-nano phase in the multi-nano phase reinforced aluminum matrix composite material is 0.5-0.6%.

2. The multi-nanophase reinforced aluminum matrix composite material according to claim 1, characterized in that, The sum of the volume percentages of ZrB2 nanoparticle reinforcing phase and Al2O3 nanoparticle reinforcing phase in the multi-nano phase reinforced aluminum matrix composite material is 3%.

3. The multi-nanophase reinforced aluminum matrix composite material according to claim 1 or 2, characterized in that, The ZrB2 nanoparticle-reinforced phase has a particle size of 80–100 nm.

4. The multi-nanophase reinforced aluminum matrix composite material according to claim 1, characterized in that, The particle size of the Al2O3 nanoparticle-reinforced phase is 80–100 nm.

5. The method for preparing the multi-nanophase reinforced aluminum matrix composite material according to any one of claims 1 to 4, characterized in that, Includes the following steps: K2ZrF6 and Na2B4O were mixed and ground to obtain powder; The powder was mixed with pure aluminum and reacted in situ to obtain a (ZrB2+Al2O3) / Al nanoparticle composite melt. After cooling, the (ZrB2+Al2O3) / Al nanoparticle composite melt is mixed with a matrix aluminum master alloy, an Al-Er rare earth alloy and an Al-Y rare earth alloy for coupling strengthening to obtain a multi-nano phase strengthened aluminum matrix composite melt. The multi-nano phase reinforced aluminum matrix composite melt is sequentially subjected to casting, plastic forming, and heat treatment to obtain the multi-nano phase reinforced aluminum matrix composite material.

6. The preparation method according to claim 5, characterized in that, The mass ratio of K2ZrF6 to Na2B4O is 0.41 to 0.43:

1.

7. The preparation method according to claim 5, characterized in that, The in-situ reaction was carried out at a temperature of 830–850 °C for 25–30 min.

8. The preparation method according to claim 5, characterized in that, The particle size of the powder is 200-250 mesh.

9. The preparation method according to claim 5, characterized in that, The coupling enhancement temperature is 700–800℃, and the time is 25–35 min.

10. The application of the multi-nano phase reinforced aluminum matrix composite material according to any one of claims 1 to 4 or the multi-nano phase reinforced aluminum matrix composite material prepared by the preparation method according to any one of claims 5 to 9 in pipe materials.

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