High-toughness in-situ ternary hybrid reinforced aluminum matrix composite material and preparation method thereof

Abstract

The application provides a high-toughness in-situ ternary hybrid reinforced aluminum matrix composite material and a preparation method thereof, a ternary hybrid reinforced system of TiB2-TiC-ZrB2 is constructed by introducing ZrB2 as a third reinforcing phase, the synergistic effect of the three ceramic phases is utilized to effectively make up for the deficiency of single or double-phase reinforcement, and the comprehensive mechanical properties of the material are significantly improved; meanwhile, a new reaction system composed of aluminum-titanium intermediate alloy, B4C and ZrSiO4 is adopted, three reinforcing particles are synchronously generated in-situ in the aluminum melt, the synergistic effect of electromagnetic stirring and ultrasonic auxiliary technology is combined, the distribution uniformity of the reinforcing particles in the matrix is significantly improved, and the agglomeration is effectively reduced, and then a thermal mechanical treatment is additionally used to further optimize the microstructure of the material, so that the tensile strength and elongation of the material are both significantly enhanced while the process feasibility is maintained, and the material has better high-temperature stability and wear resistance.

Description

Technical Field

[0001] This invention relates to the field of composite material technology, and in particular to a high-strength and tough in-situ ternary hybrid reinforced aluminum matrix composite material and its preparation method. Background Technology

[0002] Aluminum-based composites, due to their high specific strength, specific stiffness, and specific modulus, have broad application prospects in aerospace, aviation, automotive, and electronics industries. Traditional methods for preparing aluminum-based composites mainly involve adding reinforcing particles, such as SiC or Al2O3 particles, directly into the aluminum alloy melt. However, the wettability between the added reinforcing particles and the aluminum matrix is ​​usually poor, making it difficult to precisely control the interfacial reaction. The surface of the reinforcing particles is easily contaminated, and the particle distribution is uneven, leading to agglomeration. These problems seriously affect the uniformity and stability of the composite material. Furthermore, the preparation process of added particles is complex and costly, limiting its large-scale application. To address these issues, researchers have developed in-situ synthesis technology, which generates reinforcing particles, such as TiB2 and TiC, through chemical reactions in the melt. These in-situ generated particles have the advantages of clean interfaces and good bonding with the matrix.

[0003] Chinese patent publication CN1376805A discloses a method for preparing in-situ Al2O3 and TiB2 particle-reinforced aluminum matrix composites using powder sintering. However, this process employs a pure powder metallurgy route, which suffers from high raw material costs, complex process flow (including multiple steps such as powder mixing, cold pressing, sintering, and extrusion), and the inability to achieve large-scale production. In recent years, researchers have attempted to directly synthesize biphase reinforcing particles, such as the TiB2-TiC system, in melt to obtain better overall performance.

[0004] However, existing in-situ dual-phase reinforced aluminum matrix composites still face challenges such as insufficient toughness and limited high-temperature performance. This is mainly due to the limited variety of reinforcing phases, the need to improve the uniformity of particle distribution, and the insufficient refinement of the matrix structure. Especially at high temperatures, the interfacial stability between the reinforcing particles and the matrix, as well as the ability of the particles to hinder dislocation movement, become key factors restricting the improvement of material performance. In addition, traditional mechanical stirring methods are unable to completely solve the problem of agglomeration of nanoscale reinforcing particles, resulting in significant loss of plasticity in the material.

[0005] Therefore, how to achieve uniform distribution of reinforcing particles and refinement of microstructure by introducing new reinforcing phases and optimizing preparation processes while maintaining process feasibility, thereby obtaining aluminum-based composite materials with high strength, good toughness and excellent high-temperature stability, has become a technical problem that urgently needs to be solved in this field. Summary of the Invention

[0006] The purpose of this invention is to provide a high-strength and tough in-situ ternary hybrid reinforced aluminum matrix composite material and its preparation method, so as to solve the problems existing in the prior art.

[0007] To achieve the above objectives, the present invention provides the following solution:

[0008] This invention provides a high-strength and tough in-situ ternary hybrid reinforced aluminum matrix composite material, the composition and weight percentage of which are: Si 0-15%, Cu 0-8%, Mg 0-5%, TiB2 particles 0.1-15%, TiC particles 0.1-10%, ZrB2 particles 0.1-10%, and the balance being Ce and Al.

[0009] This invention also provides a method for preparing a high-strength and tough in-situ ternary hybrid reinforced aluminum matrix composite material, comprising the following steps:

[0010] 1. Add industrial pure aluminum to a crucible, heat until melted, raise the temperature to 800-1200℃, add alloying elements Si, Cu and Mg under argon protection, and stir until uniform;

[0011] 2. Mix aluminum-titanium master alloy powder, B4C particles and ZrSiO4 powder, add 0.05-0.5% Ce2O3, mix evenly and then dry; In this application, Ce2O3 accelerates and optimizes the synchronous in-situ generation of TiB2–TiC–ZrB2 ternary reinforcing phase through multiple functions such as variable valence catalysis, improved interface wetting, melt purification and particle refinement, and its residues are dissolved in the matrix or form beneficial intermetallic compounds in extremely low amounts, which has no negative impact on material properties, but can play a role in microalloying.

[0012] 3. The mixture is injected into the melt using a rotary jetting device for refining aluminum alloy, while argon gas is introduced. Electromagnetic stirring and ultrasonic-assisted treatment are started. After the reaction is completed, the rotary jetting device is removed.

[0013] 4. After settling, skim off any scum and pour the mixture into the mold;

[0014] 5. Perform thermomechanical treatment on the ingot.

[0015] Preferably, the mass ratio of the aluminum-titanium master alloy powder, B4C particles and ZrSiO4 powder in step 2 is 1:0.25-1:4:0.1-1.5.

[0016] Preferably, the drying temperature in step 2 is 100-300℃ and the drying time is 1-3 hours.

[0017] Preferably, the argon flow rate in step 3 is 10-100 ml / min.

[0018] Preferably, the electromagnetic stirring speed in step 3 is 100-800 rpm, and the stirring time is 5-30 min.

[0019] Preferably, the ultrasonic-assisted processing power in step 3 is 500-2000 W and the frequency is 20-40 kHz.

[0020] Preferably, the settling temperature in step 4 is 680-760℃, and the settling time is 5-30 minutes.

[0021] Preferably, the thermomechanical treatment in step 5 is one or more of hot extrusion, hot rolling, or hot forging.

[0022] Preferably, step 5 is followed by a T6 heat treatment step.

[0023] The present invention achieves the following beneficial technical effects compared to the prior art:

[0024] This invention provides a high-strength and tough in-situ ternary hybrid reinforced aluminum matrix composite material and its preparation method. This method, by introducing ZrB2 as a third reinforcing phase, constructs a TiB2-TiC-ZrB2 ternary hybrid reinforcement system. The synergistic effect of the three ceramic phases effectively compensates for the deficiencies of single or dual-phase reinforcement, significantly improving the overall mechanical properties of the material. Simultaneously, a novel reaction system composed of an aluminum-titanium master alloy, B4C, and ZrSiO4 is used to simultaneously generate the three reinforcing particles in situ within the aluminum melt. The combined effect of electromagnetic stirring and ultrasonic-assisted technology significantly improves the uniformity of the reinforcing particle distribution in the matrix and effectively reduces agglomeration. Further thermomechanical treatment optimizes the material's microstructure, resulting in significantly enhanced tensile strength and elongation while maintaining process feasibility, along with superior high-temperature stability and wear resistance. This effectively solves the problems of insufficient toughness and limited high-temperature performance in the original patented material, providing a better option for manufacturing high-performance structural components, demonstrating outstanding technological progress and promising prospects for industrial application. Detailed Implementation

[0025] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0026] The purpose of this invention is to provide a high-strength and tough in-situ ternary hybrid reinforced aluminum matrix composite material and its preparation method, so as to solve the problems existing in the prior art.

[0027] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, the present invention will be further described in detail below with reference to specific embodiments.

[0028] Example 1

[0029] This embodiment provides a high-strength and tough in-situ ternary hybrid reinforced aluminum matrix composite material, the composition and weight percentage of which are: Si 12%, Cu 1.0%, Mg 0.2%, TiB2 particles 8%, TiC particles 5%, ZrB2 particles 3%, and the balance being Ce and Al.

[0030] The preparation process is as follows: Industrial pure aluminum ingots are added to a crucible and heated to melt. Silicon, copper, and magnesium alloying elements are then added. The melt is protected by argon gas and the temperature is raised to 1100℃. Aluminum-titanium master alloy powder is then added... Powdered B4C and ZrSiO4 were uniformly mixed at a mass ratio of 3:1:0.8. 0.1% Ce2O3 was added, and the mixture was thoroughly mixed. The mixture was then dried at 150℃ for 2 hours, resulting in an aluminum-titanium master alloy powder with a titanium weight percentage of approximately 20%. The mixture was injected into the melt using a rotary jetting device for aluminum alloy refining, while argon gas was introduced at a flow rate of 75 ml / min. Electromagnetic stirring was activated at 250 rpm for 15 minutes; ultrasonic assisted treatment was also initiated at a power of 1000 W and a frequency of 20 kHz. After the reaction was complete, the mixture was removed from the rotary jetting device, allowed to stand at 720℃ for 10 minutes, and then the slag was removed before pouring it into a mold. The ingot was then subjected to hot extrusion treatment at an extrusion ratio of 10:1 and an extrusion temperature of 450℃. Finally, T6 heat treatment was performed (solution treatment temperature of 530℃, holding for 6 hours followed by water quenching; artificial aging temperature of 170℃, holding for 8 hours) to obtain a high-strength and tough in-situ ternary hybrid reinforced aluminum matrix composite material.

[0031] The composite material prepared in this embodiment has the following room temperature mechanical properties: tensile strength 452 MPa, yield strength 405 MPa, elongation 3.8%, and elastic modulus 96 GPa. The high temperature (300℃) tensile strength is 312 MPa.

[0032] Example 2

[0033] This embodiment provides a high-strength and tough in-situ ternary hybrid reinforced aluminum matrix composite material, the composition and weight percentage of which are: Cu 5%, TiB2 particles 5%, TiC particles 2.5%, ZrB2 particles 2.5%, and the balance being Ce and Al.

[0034] The preparation process is as follows: After melting aluminum ingots, copper alloying elements are added, and the melt is protected by argon gas and heated to 900℃. Aluminum-titanium master alloy powder, B4C particles, and ZrSiO4 powder are uniformly mixed at a mass ratio of 1:1:0.5. 0.2% Ce2O3 is added, and the mixture is thoroughly mixed and dried at 200℃ for 1 hour. The mixture is injected into the melt using a rotary jet injector with an argon gas flow rate of 30 ml / min. Electromagnetic stirring is started at 300 rpm for 10 minutes; simultaneously, ultrasonic-assisted treatment is activated at a power of 800 W and a frequency of 30 kHz. After the reaction is complete, the mixture is allowed to stand for 5 minutes at a temperature of 700℃. After removing slag, the ingot is poured. The ingot is then hot-rolled at a total deformation of 60% at a rolling temperature of 400℃. Then, T6 heat treatment was performed (solution treatment temperature of 520℃, holding for 4 hours followed by water quenching; artificial aging temperature of 160℃, holding for 6 hours).

[0035] The composite material prepared in this embodiment has the following room temperature mechanical properties: tensile strength 468 MPa, yield strength 425 MPa, elongation 3.2%, and elastic modulus 94 GPa. At high temperature (300℃), the tensile strength is 325 MPa.

[0036] Example 3

[0037] This embodiment provides a high-strength and tough in-situ ternary hybrid reinforced aluminum matrix composite material, the composition and weight percentage of which are: Si 0.5%, Mg 1.0%, TiB2 particles 8%, TiC particles 5%, ZrB2 particles 4%, and the balance being Ce and Al.

[0038] The preparation process is as follows: After melting aluminum ingots, silicon and magnesium alloying elements are added, and the melt is protected by argon gas and heated to 1000℃. Aluminum-titanium master alloy powder, B4C particles, and ZrSiO4 powder are uniformly mixed at a mass ratio of 2:1:1.2. 0.15% Ce2O3 is added, and the mixture is thoroughly mixed and dried at 200℃ for 1.5 hours. The mixture is injected into the melt using a rotary jet injector with an argon gas flow rate of 50 ml / min. Electromagnetic stirring is started at 300 rpm for 10 minutes; simultaneously, ultrasonic-assisted treatment is activated at a power of 1200 W and a frequency of 25 kHz. After the reaction is complete, the mixture is allowed to stand for 5 minutes at a standing temperature of 710℃. After removing slag, the ingot is poured. The ingot is then hot-forged at a forging ratio of 4:1 and a forging temperature of 420℃. Then, T6 heat treatment was performed (solution treatment temperature of 535℃, holding for 5 hours followed by water quenching; artificial aging temperature of 165℃, holding for 7 hours).

[0039] The composite material prepared in this embodiment has the following room temperature mechanical properties: tensile strength 478 MPa, yield strength 438 MPa, elongation 3.5%, and elastic modulus 97 GPa. The high temperature (300℃) tensile strength is 338 MPa.

[0040] Comparative Example 1

[0041] This comparative example was prepared according to the scheme of Example 1 in Chinese Patent Application No. 201410585914.9. The composition and weight percentage were: Si 12%, Cu 1.0%, Mg 0.2%, TiB2 particles 10%, TiC particles 5%, and the balance being Ce and Al. No ZrSiO4 powder was added during the preparation process, and no electromagnetic stirring, ultrasonic-assisted treatment, or thermomechanical treatment was performed. The remaining steps were the same as in Example 1.

[0042] The composite material prepared in this comparative example was tested and found to have the following room temperature mechanical properties: tensile strength 358 MPa, yield strength 316 MPa, elongation 0.7%, and elastic modulus 88 GPa. The high temperature (300℃) tensile strength was 205 MPa.

[0043] Comparative Example 2

[0044] This comparative example uses the same components as Example 1, but only electromagnetic stirring is used in the preparation process, and ultrasonic-assisted treatment is not turned on. The remaining steps are the same as in Example 1.

[0045] The composite material prepared in this comparative example was tested and found to have the following room temperature mechanical properties: tensile strength 398 MPa, yield strength 352 MPa, elongation 2.1%, and elastic modulus 91 GPa. The high temperature (300℃) tensile strength was 268 MPa.

[0046] Comparative Example 3

[0047] This comparative example uses the same components and preparation process as Example 1, but does not undergo thermomechanical treatment; the remaining steps are the same as in Example 1.

[0048] The composite material prepared in this comparative example was tested and found to have the following room temperature mechanical properties: tensile strength 412 MPa, yield strength 365 MPa, elongation 2.8%, and elastic modulus 92 GPa. The high temperature (300℃) tensile strength was 285 MPa.

[0049] Performance Comparison Analysis

[0050] The mechanical properties of Examples 1-3 and Comparative Examples 1-3 were compared, and the results are shown in Table 1.

[0051] Table 1 Comparison of mechanical properties between the examples and comparative examples

[0052] Example 1 452 405 3.8 96 312 Example 2 468 425 3.2 94 325 Example 3 478 438 3.5 97 338 Comparative Example 1 358 316 0.7 88 205 Comparative Example 2 398 352 2.1 91 268 Comparative Example 3 412 365 2.8 92 285

[0053] As shown in Table 1, the ternary hybrid reinforced aluminum matrix composites prepared in Examples 1-3 of this invention exhibit a tensile strength increase of over 26%, an elongation increase of over 4 times, and significant improvements in elastic modulus and high-temperature strength compared to the original patented biphase reinforced material of Comparative Example 1. Compared to Comparative Example 2 (electromagnetic stirring only) and Comparative Example 3 (no thermomechanical treatment), the overall performance of the examples is superior, demonstrating the significant effect of the synergistic effect of electromagnetic stirring and ultrasonic assistance, as well as thermomechanical treatment, on improving material properties. Microstructural observation shows that the reinforcing particles in the examples are uniformly distributed, without obvious agglomeration, with refined matrix grains and clean, well-bonded interfaces.

[0054] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0055] It should be noted that the components mentioned in the above embodiments are all general standard parts or components known to those skilled in the art. Their structures and principles can be learned by those skilled in the art through technical manuals or conventional experimental methods.

[0056] This invention has used specific examples to illustrate its principles and implementation methods. The above descriptions of the embodiments are merely for the purpose of helping to understand the method and core ideas of this invention. Furthermore, those skilled in the art will recognize that, based on the ideas of this invention, there will be changes in the specific implementation methods and application scope. Therefore, the content of this specification should not be construed as a limitation of this invention.

Claims

1. A high-strength and tough in-situ ternary hybrid reinforced aluminum matrix composite material, characterized in that, Its composition and weight percentage are: Si 0-15%, Cu 0-8%, Mg 0-5%, TiB2 particles 0.1-15%, TiC particles 0.1-10%, ZrB2 particles 0.1-10%, with the balance being Ce and Al.

2. A method for preparing a high-strength and tough in-situ ternary hybrid reinforced aluminum matrix composite material, characterized in that, Includes the following steps: S1. Add industrial pure aluminum to a crucible, heat until melted, raise the temperature to 800-1200℃, add alloying elements Si, Cu and Mg under argon protection, and stir evenly; S2. Mix aluminum-titanium master alloy powder, B4C particles and ZrSiO4 powder, add 0.05-0.5% Ce2O3, mix evenly and then dry; S3. Inject the mixture into the melt using a rotary jetting device for refining aluminum alloy, while simultaneously introducing argon gas, and turn on electromagnetic stirring and ultrasonic assisted treatment. After the reaction is completed, remove the rotary jetting device. S4. After settling, remove the slag and pour into the mold; S5. Perform thermomechanical treatment on the ingot.

3. The method for preparing high-strength and tough in-situ ternary hybrid reinforced aluminum matrix composite material according to claim 2, characterized in that, The mass ratio of aluminum-titanium master alloy powder, B4C particles and ZrSiO4 powder in step S2 is 1:0.25-1:4:0.1-1.

5.

4. The method for preparing high-strength and tough in-situ ternary hybrid reinforced aluminum matrix composite material according to claim 2, characterized in that, The drying temperature in step S2 is 100-300℃, and the drying time is 1-3 hours.

5. The method for preparing high-strength and tough in-situ ternary hybrid reinforced aluminum matrix composite material according to claim 2, characterized in that, The argon flow rate mentioned in step S3 is 10-100 ml / min.

6. The method for preparing high-strength and tough in-situ ternary hybrid reinforced aluminum matrix composite material according to claim 2, characterized in that, The electromagnetic stirring speed in step S3 is 100-800 rpm, and the stirring time is 5-30 min.

7. The method for preparing high-strength and tough in-situ ternary hybrid reinforced aluminum matrix composite material according to claim 2, characterized in that, The ultrasonic-assisted processing power in step S3 is 500-2000 W, and the frequency is 20-40 kHz.

8. The method for preparing high-strength and tough in-situ ternary hybrid reinforced aluminum matrix composite material according to claim 2, characterized in that, The settling temperature in step S4 is 680-760℃, and the settling time is 5-30 minutes.

9. The method for preparing high-strength and tough in-situ ternary hybrid reinforced aluminum matrix composite material according to claim 2, characterized in that, The thermomechanical treatment described in step S5 is one or more of hot extrusion, hot rolling, or hot forging, followed by T6 heat treatment.