High-toughness tin-based quaternary alloy and preparation method thereof
By introducing hafnium and yttrium into tin-based alloys and combining ultrasonic vibration, electromagnetic stirring and multi-stage aging treatment, a Sn-Cu-Hf-Y quaternary alloy was constructed, which solved the problem of easy failure of tin-based alloys under high load or high speed and achieved a synergistic improvement in high strength and high toughness.
Patent Information
- Application Number
- CN202511414822.9
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-09-30
- Publication Date
- 2026-01-09
AI Technical Summary
Existing tin-based alloys are prone to early failure under high load or high speed conditions, and have low strength and insufficient toughness. Traditional preparation processes cannot achieve a synergistic improvement in strength, toughness and plasticity.
By introducing specific proportions of hafnium (Hf) and yttrium (Y) elements, and combining ultrasonic vibration, low-frequency electromagnetic stirring and high-frequency alternating magnetic field, a Sn-Cu-Hf-Y quaternary high-performance system was constructed through rapid solidification by the belt spinning method and multi-stage aging treatment.
It significantly improves the yield strength, tensile strength and elongation of the alloy, achieving a balance between high strength and high toughness, with a yield strength ≥300 MPa, tensile strength ≥450 MPa and elongation ≥25%.
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Abstract
Description
Technical Field
[0001] This invention relates to the field of alloy technology, and in particular to a high-strength and high-toughness tin-based quaternary alloy and its preparation method. Background Technology
[0002] Tin-based alloys are widely used in sliding bearings, solders, and electronic packaging due to their excellent thermal conductivity, lubricity, good casting properties, and environmental friendliness. Traditional tin-based bearing alloys are mostly Sn-Sb-Cu or Sn-Pb-Cu systems, with their wear resistance and strength improved through micro-adjustments of alloying elements. However, these alloys generally suffer from low strength, insufficient toughness, and poor heat resistance, making them prone to premature failure, especially under high load or high speed conditions.
[0003] In recent years, researchers have attempted to improve the mechanical properties of tin-based alloys by introducing rare earth elements, transition metals, or employing composite strengthening methods. For example, adding trace amounts of rare earth elements such as Ce and La can refine the grains and improve the uniformity of the microstructure to some extent. However, rare earth elements are sensitive to oxidation, difficult to prepare, and have poor stability in mass production. Another type of modification involves introducing transition metal elements such as Ti, Zr, and V, aiming to improve their overall performance through solid solution strengthening or second-phase dispersion strengthening. However, these metals have limited solubility in tin and are prone to segregation or the formation of coarse intermetallic compounds during solidification, thus affecting the consistency and stability of the material.
[0004] Furthermore, existing manufacturing processes mostly rely on traditional casting and conventional heat treatment, lacking precise control over key processes such as solidification behavior, grain size regulation, and metastable phase formation, making it difficult to simultaneously improve strength, toughness, and plasticity. Especially in grain refinement and multi-scale microstructure construction, traditional methods depend on external deformation or multi-step heat treatment, resulting in high energy consumption, large microstructure fluctuations, and high control difficulty, thus limiting the further application of tin-based alloys in high-performance applications.
[0005] Therefore, how to achieve a balance between high strength and high toughness in tin-based alloys while maintaining good machinability and economy has become an important technical problem that urgently needs to be solved in this field. Summary of the Invention
[0006] Based on the technical problems existing in the background technology, the present invention proposes a high-strength and high-toughness tin-based quaternary alloy and its preparation method. The prepared tin-based quaternary alloy has excellent strength and toughness.
[0007] The present invention proposes a high-strength and high-toughness tin-based quaternary alloy, characterized in that it contains the following components by weight percentage: 1-5% copper, 0.1-0.5% hafnium, 0.05-0.15% yttrium, with the balance being tin and unavoidable impurities.
[0008] Preferably, the tin-based quaternary alloy has a yield strength ≥300MPa, a tensile strength ≥450MPa, and an elongation ≥25%.
[0009] Preferably, the sum of the weight percentages of hafnium and yttrium is not greater than 0.5%, and the impurity content is ≤0.05%.
[0010] The present invention proposes a method for preparing the above-mentioned high-strength and high-toughness tin-based quaternary alloy, the method steps of which are as follows: S1: Weigh the raw materials according to the weight percentage and melt them in a vacuum induction furnace to obtain melt M1; S2: Cool the melt M1 into the semi-solid region, and simultaneously apply ultrasonic vibration and low-frequency electromagnetic stirring to obtain the semi-solid melt M2. S3: The semi-solid melt M2 is rapidly solidified under a high-frequency alternating magnetic field by a strip spinning method to obtain strip billet M3; S4: Hot isostatic pressing is applied to strip billet M3 to obtain dense billet M4; S5: Perform solution heat treatment on the dense blank M4 to obtain solid solution M5; S6: Keep solid solution M5 at 150-170℃ for 1-3 hours to obtain primary aging product M6; S7: The first-aged product M6 is kept at 115-125℃ for 6-10 hours to obtain the second-aged product M7. S8: The secondary aging product M7 is kept at 90-100℃ for 12-24h to obtain a high-strength and high-toughness tin-based quaternary alloy.
[0011] Preferably, the smelting conditions in S1 are: in an inert atmosphere, a temperature of 1100-1200℃, and a pressure of 0.03-0.05MPa.
[0012] Preferably, the temperature at which the material cools into the semi-solid region in S2 is 240-260℃; the frequency of the ultrasonic vibration is 15-25kHz; the magnetic field strength of the low-frequency electromagnetic field is 0.05-0.10T; and the stirring time is 1-2min.
[0013] Preferably, the frequency of the high-frequency alternating magnetic field in S3 is 200-600kHz; the cooling rate for the rapid solidification of the semi-solid melt M2 is 30-60℃ / s.
[0014] Preferably, the conditions for hot isostatic pressing in S4 are: temperature 150-200℃, pressure 700-900MPa, and time 5-15min.
[0015] Preferably, the solution heat treatment in S5 is performed at a temperature of 200-220°C for 30-60 minutes.
[0016] Beneficial technical effects of the present invention: (1) This invention introduces a specific proportion of hafnium (Hf) and yttrium (Y) elements into the traditional tin-based alloy to construct a Sn-Cu-Hf-Y quaternary high-performance system, which realizes the synergistic improvement of the alloy's strength, toughness and plasticity, and significantly improves the problems of low yield strength, poor ductility and weak thermal stability of existing tin-based alloys. Among them, the addition of hafnium and yttrium can not only form a high-melting-point and high-stability dispersed strengthening phase in the tin matrix to hinder dislocation movement and improve the alloy's yield strength and thermal stability, but also promote grain refinement, inhibit dendrite growth during solidification, optimize the crystal structure, and improve the alloy's toughness and crack resistance. Through the synergistic effect of hafnium and yttrium, a balance is achieved between the generation of strengthening phase and plastic loss, which ensures both high strength and high elongation, so that the obtained alloy has a yield strength ≥300 MPa, tensile strength ≥450 MPa and elongation ≥25%.
[0017] (2) In terms of preparation method, the present invention effectively breaks the crystal nuclei, strengthens convection, and accelerates uniform composition distribution by applying ultrasonic vibration and low-frequency electromagnetic stirring in the semi-solid region, thereby refining the primary crystal size and suppressing macroscopic segregation; the strip spinning method is used to rapidly solidify under a high-frequency alternating magnetic field, which can obtain fine and uniform strip blanks, effectively control the undercooling of the structure, facilitate the precipitation of metastable phases and improve the overall density; the subsequent hot isostatic pressing treatment and multi-stage aging work together to promote the dispersion precipitation of fine strengthening phases, constructing a submicron-level fine-grained structure and a dual-strength structure of second-phase particles, which significantly improves the resistance to deformation and crack propagation resistance. Detailed Implementation
[0018] The present invention will be further described below with reference to specific embodiments. Example 1
[0019] Weigh the raw materials according to the following weight percentages: copper 3%, hafnium 0.3%, yttrium 0.1%, balance tin and unavoidable impurities (≤0.05%). Melt the raw materials in a vacuum induction furnace at 1150°C under an inert atmosphere and control the pressure at 0.04 MPa to obtain melt M1-1.
[0020] The melt M1-1 was cooled to 250°C and entered the semi-solid region. At the same time, 20kHz ultrasonic vibration and 0.08T low-frequency electromagnetic stirring were applied for 1.5 minutes to obtain semi-solid melt M2-1.
[0021] The semi-solid melt M2-1 was rapidly solidified under a 400kHz high-frequency alternating magnetic field by a strip spinning method at a cooling rate of 45℃ / s to obtain strip billet M3-1. The strip billet M3-1 was subjected to hot isostatic pressing at 180℃ and 800MPa for 10 minutes to obtain dense billet M4-1.
[0022] The dense blank M4-1 was subjected to solution heat treatment at 210℃ for 45 min to obtain solid solution M5-1; The solid solution M5-1 was kept at 160℃ for 2 hours to obtain the first-aged product M6-1; The product M6-1, which was aged once, was kept at 120℃ for 8 hours to obtain the product M7-1, which was aged twice. The secondary aging product M7-1 was kept at 95℃ for 18 hours to obtain a high-strength and high-toughness tin-based quaternary alloy. Example 2
[0023] Weigh the raw materials according to the following weight percentages: 1% copper, 0.1% hafnium, 0.015% yttrium, with the balance being tin and unavoidable impurities. Melt the raw materials in a vacuum induction furnace at 1100°C under an inert atmosphere and a controlled pressure of 0.03 MPa to obtain melt M1-2.
[0024] The melt M1-2 was cooled to 240°C and entered the semi-solid region. At the same time, 15kHz ultrasonic vibration and 0.05T low-frequency electromagnetic stirring were applied for 1 minute to obtain semi-solid melt M2-2.
[0025] The semi-solid melt M2-2 was rapidly solidified under a 200kHz high-frequency alternating magnetic field by a strip spinning method at a cooling rate of 30℃ / s to obtain strip billet M3-2. The strip billet M3-2 was subjected to hot isostatic pressing at 150℃ and 700MPa for 5 minutes to obtain dense billet M4-2.
[0026] The dense blank M4-2 was subjected to solution heat treatment at 200℃ for 30 min to obtain solid solution M5-2; The solid solution M5-2 was kept at 150℃ for 1 hour to obtain the first-aged product M6-2; The first-aged product M6-2 was kept at 115℃ for 6 hours to obtain the second-aged product M7-2. The secondary aging product M7-2 was kept at 90℃ for 12 hours to obtain a high-strength and high-toughness tin-based quaternary alloy. Example 3
[0027] The raw materials are weighed according to the following weight percentages: 5% copper, 0.45% hafnium, 0.05% yttrium, with the balance being tin and unavoidable impurities. The raw materials are then melted in a vacuum induction furnace at 1200°C under an inert atmosphere, with the pressure controlled at 0.05 MPa, to obtain melt M1-3.
[0028] The melt M1-3 was cooled to 260°C and entered the semi-solid region. At the same time, 25kHz ultrasonic vibration and 0.10T low-frequency electromagnetic stirring were applied for 2 minutes to obtain semi-solid melt M2-3.
[0029] The semi-solid melt M2-3 was rapidly solidified under a 600kHz high-frequency alternating magnetic field by a strip spinning method at a cooling rate of 60℃ / s to obtain strip billet M3-3. The strip billet M3-3 was subjected to hot isostatic pressing at 200℃ and 900MPa for 15 minutes to obtain dense billet M4-3.
[0030] The dense blank M4-3 was subjected to solution heat treatment at 220℃ for 60 min to obtain solid solution M5-3; The solid solution M5-3 was kept at 170℃ for 3 hours to obtain the first-aged product M6-3; The first-aged product M6-3 was kept at 125℃ for 10 hours to obtain the second-aged product M7-3. The secondary aging product M7-3 was kept at 100℃ for 24 hours to obtain a high-strength and high-toughness tin-based quaternary alloy. Comparative Example 1
[0031] Weigh the raw materials according to the following weight percentages: 3% copper, 0.4% hafnium, and the balance being tin and unavoidable impurities (≤0.05%). Melt the raw materials in a vacuum induction furnace at 1150°C under an inert atmosphere and control the pressure at 0.04 MPa to obtain melt M1-4.
[0032] The melt M1-4 was cooled to 250°C and entered the semi-solid region. At the same time, 20kHz ultrasonic vibration and 0.08T low-frequency electromagnetic stirring were applied for 1.5 minutes to obtain semi-solid melt M2-4.
[0033] The semi-solid melt M2-4 was rapidly solidified under a 400kHz high-frequency alternating magnetic field by a strip spinning method at a cooling rate of 45℃ / s to obtain strip billet M3-4. The strip billet M3-4 was subjected to hot isostatic pressing at 180℃ and 800MPa for 10 minutes to obtain dense billet M4-4.
[0034] The dense blank M4-4 was subjected to solution heat treatment at 210℃ for 45 min to obtain solid solution M5-4; The solid solution M5-4 was kept at 160℃ for 2 hours to obtain the first-aged product M6-4; The first-aged product M6-4 was kept at 120℃ for 8 hours to obtain the second-aged product M7-4. The secondary aging product M7-4 was kept at 95℃ for 18 hours to obtain a high-strength and high-toughness tin-based quaternary alloy. Comparative Example 2
[0035] Weigh the raw materials according to the following weight percentages: 3% copper, 0.4% yttrium, and the balance being tin and unavoidable impurities (≤0.05%). Melt the raw materials in a vacuum induction furnace at 1150°C under an inert atmosphere and control the pressure at 0.04 MPa to obtain melt M1-5.
[0036] The melt M1-5 was cooled to 250°C and entered the semi-solid region. At the same time, 20kHz ultrasonic vibration and 0.08T low-frequency electromagnetic stirring were applied for 1.5 minutes to obtain semi-solid melt M2-5.
[0037] The semi-solid melt M2-5 was rapidly solidified under a 400kHz high-frequency alternating magnetic field by a strip spinning method at a cooling rate of 45℃ / s to obtain strip billet M3-5. The strip billet M3-5 was subjected to hot isostatic pressing at 180℃ and 800MPa for 10 minutes to obtain dense billet M4-5.
[0038] The dense blank M4-5 was subjected to solution heat treatment at 210℃ for 45 min to obtain solid solution M5-5; The solid solution M5-5 was kept at 160℃ for 2 hours to obtain the first-aged product M6-5; The first-aged product M6-5 was kept at 120℃ for 8 hours to obtain the second-aged product M7-5. The secondary aging product M7-5 was kept at 95℃ for 18 hours to obtain a high-strength and high-toughness tin-based quaternary alloy. Comparative Example 3
[0039] Weigh the raw materials according to the following weight percentages: copper 3%, hafnium 0.4%, yttrium 0.2%, with the balance being tin and unavoidable impurities (≤0.05%). Melt the raw materials in a vacuum induction furnace at 1150°C under an inert atmosphere and control the pressure at 0.04 MPa to obtain melt M1-6.
[0040] The melt M1-6 was cooled to 250°C and entered the semi-solid region. At the same time, 20kHz ultrasonic vibration and 0.08T low-frequency electromagnetic stirring were applied for 1.5 minutes to obtain semi-solid melt M2-6.
[0041] The semi-solid melt M2-6 was rapidly solidified under a 400kHz high-frequency alternating magnetic field by a strip spinning method at a cooling rate of 45℃ / s to obtain strip billet M3-6. The strip billet M3-6 was subjected to hot isostatic pressing at 180℃ and 800MPa for 10 minutes to obtain dense billet M4-6.
[0042] The dense blank M4-6 was subjected to solution heat treatment at 210℃ for 45 min to obtain solid solution M5-6; The solid solution M5-6 was kept at 160℃ for 2 hours to obtain the first-aged product M6-6; The first-aged product M6-6 was kept at 120℃ for 8 hours to obtain the second-aged product M7-6. The secondary aging product M7-6 was kept at 95℃ for 18 hours to obtain a high-strength and high-toughness tin-based quaternary alloy. Comparative Example 4
[0043] Weigh the raw materials according to the following weight percentages: copper 3%, hafnium 0.3%, yttrium 0.1%, balance tin and unavoidable impurities (≤0.05%). Melt the raw materials in a vacuum induction furnace at 1150°C under an inert atmosphere and control the pressure at 0.04 MPa to obtain melt M1-7.
[0044] The melt M1-7 was cooled to 250°C and introduced into the semi-solid region. It was then stirred with ultrasonic vibration at 20 kHz for 1.5 min to obtain the semi-solid melt M2-7.
[0045] The semi-solid melt M2-7 was rapidly solidified under a 400kHz high-frequency alternating magnetic field by a strip spinning method at a cooling rate of 45℃ / s to obtain strip billet M3-7. The strip billet M3-7 was subjected to hot isostatic pressing at 180℃ and 800MPa for 10 minutes to obtain dense billet M4-7.
[0046] The dense blank M4-7 was subjected to solution heat treatment at 210℃ for 45 min to obtain solid solution M5-7; The solid solution M5-7 was kept at 160℃ for 2 hours to obtain the first-aged product M6-7; The first-aged product M6-7 was kept at 120℃ for 8 hours to obtain the second-aged product M7-7. The secondary aging product M7-7 was kept at 95℃ for 18 hours to obtain a high-strength and high-toughness tin-based quaternary alloy. Comparative Example 5
[0047] Weigh the raw materials according to the following weight percentages: copper 3%, hafnium 0.3%, yttrium 0.1%, balance tin and unavoidable impurities (≤0.05%). Melt the raw materials in a vacuum induction furnace at 1150°C under an inert atmosphere and control the pressure at 0.04 MPa to obtain melt M1-8.
[0048] The melt M1-8 was cooled to 250°C and introduced into the semi-solid zone. Low-frequency electromagnetic stirring at 0.08T was applied for 1.5 minutes to obtain semi-solid melt M2-8.
[0049] The semi-solid melt M2-8 was rapidly solidified under a 400kHz high-frequency alternating magnetic field by a strip spinning method at a cooling rate of 45℃ / s to obtain the strip billet M3-8. The strip billet M3-8 was subjected to hot isostatic pressing at 180℃ and 800MPa for 10 minutes to obtain dense billet M4-8.
[0050] The dense blank M4-8 was subjected to solution heat treatment at 210℃ for 45 min to obtain solid solution M5-8; The solid solution M5-8 was kept at 160℃ for 2 hours to obtain the first-aged product M6-8; The first-aged product M6-8 was kept at 120℃ for 8 hours to obtain the second-aged product M7-8. The secondary aging product M7-8 was kept at 95℃ for 18 hours to obtain a high-strength and high-toughness tin-based quaternary alloy.
[0051] The yield strength, tensile strength and elongation of the tin-based quaternary alloys prepared in Examples 1-3 and Comparative Examples 1-5 were measured, and the test results are shown in Table 1.
[0052] Table 1. Performance test results of tin-based quaternary alloys
[0053] As can be seen from the test results in Table 1, this invention constructs a Sn-Cu-Hf-Y quaternary high-performance system by introducing a specific proportion of hafnium (Hf) and yttrium (Y) elements on the basis of traditional tin-based alloys. This achieves a synergistic improvement in the strength, toughness and plasticity of the alloy, and significantly improves the problems of low yield strength, poor ductility and weak thermal stability of existing tin-based alloys. The resulting alloy has a yield strength ≥300 MPa, a tensile strength ≥450 MPa and an elongation ≥25%.
[0054] As can be seen from the experimental results of Example 1 and Comparative Examples 1-2, the hafnium and yttrium added in this invention have a synergistic promoting effect on improving the strength and toughness of the alloy. This is because the addition of hafnium and yttrium can not only form a high-melting-point, high-stability dispersed strengthening phase in the tin matrix to hinder dislocation movement and improve the yield strength and thermal stability of the alloy, but also promote grain refinement, inhibit dendrite growth during solidification, optimize the crystal structure, and improve the toughness and crack resistance of the alloy. Through the synergistic effect of hafnium and yttrium, a balance is achieved between the formation of strengthening phase and plastic loss, ensuring both high strength and high elongation.
[0055] As can be seen from the test results of Example 1 and Comparative Example 3, the amount of hafnium and yttrium added also has a great influence on the strength and toughness of the alloy. When the sum of the amounts of hafnium and yttrium added exceeds 0.5% (0.6% in Comparative Example 3), it will have a great impact on the strength and toughness of the alloy.
[0056] As can be seen from the experimental results of Example 1 and Comparative Examples 4-5, when preparing the alloy, the present invention can effectively break the crystal nuclei, enhance convection, accelerate the uniform composition distribution, refine the primary crystal size and suppress macrosegregation by simultaneously applying ultrasonic vibration and low-frequency electromagnetic stirring when the melt is cooled to the semi-solid region, thereby further improving the strength and toughness of the alloy.
[0057] Although embodiments of this application have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of this application. The scope of this application is defined by the appended claims and their equivalents, all of which should be included within the protection scope of this application.
Claims
1. A high-strength and high-toughness tin-based quaternary alloy, characterized in that, It contains the following components by weight percentage: 1-5% copper, 0.1-0.5% hafnium, 0.05-0.15% yttrium, with the balance being tin and unavoidable impurities.
2. The high-strength and high-toughness tin-based quaternary alloy according to claim 1, characterized in that, The yield strength of the tin-based quaternary alloy is ≥300MPa, the tensile strength is ≥450MPa, and the elongation is ≥25%.
3. The high-strength and high-toughness tin-based quaternary alloy according to claim 1, characterized in that, The sum of the weight percentages of hafnium and yttrium is ≤0.5%, and the weight percentage of impurities is ≤0.05%.
4. A method for preparing the high-strength and high-toughness tin-based quaternary alloy according to any one of claims 1-3, characterized in that, The steps are as follows: S1: Weigh the raw materials according to the weight percentage and melt them in a vacuum induction furnace to obtain melt M1; S2: Cool the melt M1 into the semi-solid region, and simultaneously apply ultrasonic vibration and low-frequency electromagnetic stirring to obtain the semi-solid melt M2. S3: The semi-solid melt M2 is rapidly solidified under a high-frequency alternating magnetic field by a strip spinning method to obtain strip billet M3; S4: Hot isostatic pressing is applied to the strip billet M3 to obtain a dense billet M4; S5: Perform solution heat treatment on the dense blank M4 to obtain solid solution M5; S6: Keep solid solution M5 at 150-170℃ for 1-3 hours to obtain primary aging product M6; S7: The first-aged product M6 is kept at 115-125℃ for 6-10 hours to obtain the second-aged product M7. S8: The secondary aging product M7 is kept at 90-100℃ for 12-24h to obtain a high-strength and high-toughness tin-based quaternary alloy.
5. The method for preparing a high-strength and high-toughness tin-based quaternary alloy according to claim 4, characterized in that, The smelting conditions in S1 are: inert atmosphere, temperature 1100-1200℃, pressure 0.03-0.05MPa.
6. The method for preparing a high-strength and high-toughness tin-based quaternary alloy according to claim 4, characterized in that, The temperature of the semi-solid region in S2 is 240-260℃; the frequency of ultrasonic vibration is 15-25kHz; the magnetic field strength of low-frequency electromagnetic field is 0.05-0.10T; and the stirring time is 1-2min.
7. The method for preparing a high-strength and high-toughness tin-based quaternary alloy according to claim 4, characterized in that, The frequency of the high-frequency alternating magnetic field in S3 is 200-600kHz; the cooling rate of the semi-solid melt M2 for rapid solidification is 30-60℃ / s.
8. The method for preparing a high-strength and high-toughness tin-based quaternary alloy according to claim 4, characterized in that, The conditions for hot isostatic pressing in S4 are: temperature 150-200℃, pressure 700-900MPa, and time 5-15min.
9. The method for preparing a high-strength and high-toughness tin-based quaternary alloy according to claim 4, characterized in that, The solution heat treatment in S5 is performed at a temperature of 200-220℃ for 30-60 minutes.