Ni3ti reinforced copper matrix in-situ composite and preparation method thereof

Abstract

The application discloses a kind of Ni3Ti reinforced copper-based in-situ composite and preparation method thereof, belong to non-ferrous metal preparation field, the Ni3Ti reinforced copper-based in-situ composite includes micron grade Ni3Ti reinforcing phase, and according to mass percentage, it includes the following components: Ni: 2.5~3.5wt%, Ti: 0.8~1.2wt%, auxiliary element 0.1%~2.0%, the balance is Cu.This application can optimize the organization distribution of Ni3Ti reinforced copper-based in-situ composite by optimizing component and component ratio, to improve the mechanical properties and electrical conductivity of Ni3Ti reinforced copper-based in-situ composite, also can improve the high-temperature softening resistance of Ni3Ti reinforced copper-based in-situ composite, can satisfy the use requirement of high-end lead frame material.The overall tensile strength reaches 800~900MPa, the conductivity reaches 50%IACS-65%IACS, high-temperature softening temperature reaches 580 DEG C above, satisfy the application demand of high-end lead frame material.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of non-ferrous metal preparation, in particular to a Ni3Ti reinforced copper-based in-situ composite material and a preparation method thereof. BACKGROUND

[0002] Copper alloy is widely used as a key basic material in the electronic information industry with the rapid development of electronic information technology. At the same time, higher requirements are put forward for the performance of copper alloy. In the application field of integrated circuit lead frame, not only is high electrical conductivity required, but also high tensile strength and softening resistance temperature are required. However, the copper alloy for lead frame at the present stage not only has the problem of mismatching between strength and electrical conductivity, but also has the problem of low softening resistance temperature. Therefore, the development of new high-strength high-conductivity high-softening lead frame copper alloy material is a research hotspot at home and abroad.

[0003] The in-situ composite method is one of the simplest and most effective methods for preparing high-strength high-conductivity copper-based materials. At present, it is widely used in Cu-Fe, Cu-Nb, Cu-Ag and Cu-Cr alloys, such as Chinese patent CN108611520B, which discloses a preparation method of copper-based in-situ composite material. However, it deposits a carbon nanotube thin layer through a chemical vapor deposition process, and then carries out mixing smelting, casting, hot forging, solid solution treatment and cold drawing. However, the overall process is complex, and the softening temperature is low. Ni3Ti is an intermetallic compound, which is often used as a reinforcing phase in nickel-based high-temperature alloys. However, there is little research on it in copper-based alloys. In the field of preparation of copper-based alloys, there is still a problem of poor performance of alloy materials. SUMMARY

[0004] Therefore, in order to solve the problem of poor performance of alloy materials, the present application provides a Ni3Ti reinforced copper-based in-situ composite material and a preparation method thereof. The specific technical solutions are as follows:

[0005] A Ni3Ti reinforced copper-based in-situ composite material, which comprises a micron-sized Ni3Ti reinforcing phase, and according to mass percentage, the Ni3Ti reinforced copper-based in-situ composite material comprises the following components: Ni: 2.5-3.5wt%, Ti: 0.8-1.2wt%, auxiliary elements 0.1%-2.0%, and the balance is Cu.

[0006] Further, the mass percentage of Ni and Ti is (2.8-3.5): 1.

[0007] Further, the total addition amount of Ni and Ti is less than or equal to 5wt%.

[0008] Further, the auxiliary elements are one of Zr, Y and Sc, and the Zr is 0.1-0.8wt%, the Y is 0.1-0.6wt%, and the Sc is 0.1-0.6wt% according to the mass percentage.

[0009] In addition, the application provides a preparation method of the Ni3Ti reinforced copper-based in-situ composite material, and the preparation method comprises the following steps:

[0010] Cu, Ni, Ti, Zr, Y and Sc are added into a vacuum induction furnace, smelting treatment is carried out under the condition of protective gas, and then the alloy cast blank is obtained by casting;

[0011] The alloy cast blank is subjected to hot rolling treatment, solid solution treatment, multiple cold rolling treatment, and then aging treatment, so as to obtain the Ni3Ti reinforced copper-based in-situ composite material.

[0012] The temperature of the hot rolling treatment is 820-880℃, and the deformation amount is 40-60%; the deformation amount of the cold rolling treatment is greater than or equal to 80%.

[0013] Further, the temperature of the solid solution treatment is 850-950℃, and the time is 1-3h.

[0014] Further, the temperature of the aging treatment is 450-600℃, and the time is 8-12h.

[0015] Further, after the solid solution treatment, the Ni3Ti reinforced copper-based in-situ composite material is subjected to water quenching treatment, the micron-sized Ni3Ti in-situ reinforced phase is dissolved back and precipitates micron-sized Ni3Ti reinforced phase in the subsequent cooling process.

[0016] Further, after the multiple cold rolling treatment, the micron-sized Ni3Ti reinforced phase is uniformly distributed along the deformation band.

[0017] By optimizing the components and the component proportion in the above scheme, the microstructure distribution of the Ni3Ti reinforced copper-based in-situ composite material can be optimized, the mechanical properties and the electrical conductivity of the Ni3Ti reinforced copper-based in-situ composite material can be improved, the high-temperature softening resistance of the Ni3Ti reinforced copper-based in-situ composite material can be improved, and the use requirements of high-end lead frame materials can be met. Specifically, by controlling the total amount (≤5 wt%) and the proportion of Ni and Ti, micron-sized Ni3Ti in-situ reinforced phases are formed, the morphology and distribution of the Ni3Ti are effectively controlled by adding Zr, Y and Sc elements, and the mechanical properties and the electrical conductivity of the alloy are significantly improved by combining the precise control of the deformation process and the aging process. The improvement of the electrical conductivity of the alloy is attributed to the precipitation of nanoscale Ni3Ti phases. In addition, the addition of one of Zr, Y and Sc not only improves the morphology and distribution of the micron-sized Ni3Ti phases, but also has a certain inhibitory effect on the recovery and recrystallization behavior of the alloy in a high-temperature environment, thereby improving the over-aging resistance and the high-temperature softening resistance of the alloy. In addition, the Ni3Ti reinforced copper-based in-situ composite material is prepared by combining various strengthening methods such as vacuum melting, hot rolling, solid solution, multi-pass cold rolling and aging treatment, and the performance of the Ni3Ti reinforced copper-based in-situ composite material is significantly improved. The tensile strength of the Ni3Ti reinforced copper-based in-situ composite material is 800-900 MPa, the electrical conductivity is 50% IACS-65% IACS, the high-temperature softening resistance temperature is above 580℃, and the application requirements of high-end lead frame materials are met. BRIEF DESCRIPTION OF DRAWINGS

[0018] Figure 1 A metallographic schematic diagram of the Cu-3Ni-1Ti-0.5Zr alloy prepared in Example 1 after cold rolling by 90%;

[0019] Figure 2 A metallographic schematic diagram of the Cu-3Ni-1Ti-0.2Y alloy prepared in Example 2 after cold rolling by 90%;

[0020] Figure 3 A metallographic schematic diagram of the Cu-3Ni-1Ti-0.3Sc alloy prepared in Example 3 after cold rolling by 90%;

[0021] Figure 4 A tensile stress-strain curve schematic diagram of the Cu-3Ni-1Ti-0.3Sc alloy after cold rolling by 90% at 500℃ for different times. DETAILED DESCRIPTION

[0022] In order to make the purpose, technical scheme and advantages of the present application more clear and explicit, the present application will be further described in detail below in combination with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and do not limit the protection scope of the present application.

[0023] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used in the description herein is for describing particular embodiments only and is not intended to be limiting of the application. As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items.

[0024] The Ni3Ti reinforced copper-based in-situ composite material in an embodiment of the application comprises a micron-sized Ni3Ti reinforcing phase, and comprises the following components in terms of mass percentage: Ni: 2.5-3.5 wt%, Ti: 0.8-1.2 wt%, auxiliary elements 0.1%-2.0%, and the balance being Cu.

[0025] In one embodiment, the mass percentage of Ni and Ti is (2.8-3.5): 1.

[0026] In one embodiment, the total amount of Ni and Ti added is less than or equal to 5 wt%.

[0027] In one embodiment, the auxiliary elements are one of Zr, Y, and Sc, and Zr: 0.1-0.8 wt%, Y: 0.1-0.6 wt%, and Sc: 0.1-0.6 wt% in terms of mass percentage.

[0028] In addition, the application provides a preparation method of a Ni3Ti reinforced copper-based in-situ composite material, which comprises the following steps:

[0029] Cu, Ni, Ti, Zr, Y, and Sc are added to a vacuum induction furnace, smelting treatment is performed under the condition of a protective gas, and then the alloy cast blank is obtained by casting;

[0030] The alloy cast blank is subjected to hot rolling treatment, solid solution treatment, multiple cold rolling treatment, and then aging treatment, to obtain a Ni3Ti reinforced copper-based in-situ composite material;

[0031] In the hot rolling treatment, the temperature is 820-880°C, and the deformation amount is 40%-60%; in the cold rolling treatment, the deformation amount is greater than or equal to 80%.

[0032] In one embodiment, the temperature of the solid solution treatment is 850-950°C, and the time is 1-3 h.

[0033] In one embodiment, the temperature of the aging treatment is 450-600°C, and the time is 8-12 h.

[0034] In one of the embodiments, after the solution treatment, the micro-sized Ni3Ti in-situ reinforced phase is dissolved and precipitates during the subsequent cooling process.

[0035] In one of the embodiments, after the multiple cold rolling treatment, the micro-sized Ni3Ti reinforced phase is uniformly distributed along the deformation zone.

[0036] The above scheme can optimize the microstructure distribution of the Ni3Ti reinforced copper-based in-situ composite by optimizing the composition and the proportion of the components, so as to improve the mechanical properties and the electrical conductivity of the Ni3Ti reinforced copper-based in-situ composite, and improve the high-temperature softening resistance of the Ni3Ti reinforced copper-based in-situ composite, so as to meet the use requirements of high-end lead frame materials. Specifically, by controlling the total amount (≤5wt%) and the proportion of Ni and Ti, the micro-sized Ni3Ti in-situ reinforced phase is formed, and by adding Zr, Y and Sc elements, the morphology and distribution of Ni3Ti are effectively controlled, and by accurately controlling the deformation process and aging process, the mechanical properties and the electrical conductivity of the alloy are significantly improved. The improvement of the electrical conductivity of the alloy is attributed to the precipitation of the nano-sized Ni3Ti phase. In addition, the addition of one of Zr, Y and Sc not only improves the morphology and distribution of the micro-sized Ni3Ti phase, but also has a certain inhibitory effect on the recovery and recrystallization behavior of the alloy in a high-temperature environment, thereby improving the over-aging resistance and high-temperature softening resistance of the alloy. In addition, the Ni3Ti reinforced copper-based in-situ composite is prepared by combining a plurality of strengthening methods such as vacuum melting, hot rolling, solution, multiple cold rolling and aging treatment, which significantly improves the performance of the Ni3Ti reinforced copper-based in-situ composite. The tensile strength of the Ni3Ti reinforced copper-based in-situ composite is 800-900 MPa, the electrical conductivity is 50% IACS-65% IACS, the high-temperature softening resistance is above 580℃, and the application requirements of high-end lead frame materials are met.

[0037] The embodiments of the present application will be described in detail below with reference to specific examples.

[0038] Example 1:

[0039] A preparation method of a Ni3Ti reinforced copper-based in-situ composite, comprising the following steps:

[0040] According to the mass percentage, 3.5% Ni, 1.2% Ti, 0.5 Zr, and the balance Cu are proportioned, and the alloy ingot is obtained by argon protection melting in a vacuum induction melting furnace and graphite mold casting;

[0041] Hot rolling treatment: the ingot is hot rolled at 850℃ for 3h, and the hot rolling deformation is 50%;

[0042] Solution treatment: The hot-rolled alloy was solution treated at 850℃ for 1 hour and then rapidly water-cooled to obtain a supersaturated solid solution;

[0043] Cold rolling: The alloy after solution treatment is cold rolled in multiple passes to achieve a deformation of up to 90%;

[0044] Aging treatment: The cold-rolled alloy was placed in a resistance furnace and aged at 500℃ for 15 hours to obtain Ni3Ti reinforced copper-based in-situ composite material.

[0045] like Figure 1 As shown, the in-situ test of Ni3Ti reinforced copper-based composite material was conducted from... Figure 1 A large number of micron-sized Ni3Ti in-situ reinforcing phases can be observed in the alloy. The excellent mechanical properties of the alloy are attributed to the interaction between the micron-sized Ni3Ti in-situ reinforcing phases and dislocations, while the improved conductivity of the alloy is attributed to the aging precipitation of nano-sized Ni3Ti phases.

[0046] Example 2:

[0047] A method for preparing a Ni3Ti-reinforced copper-based in-situ composite material includes the following steps:

[0048] According to the mass percentage, 3.2% Ni, 1.1% Ti, 0.2% Y, and the balance Cu are batched and melted in a vacuum induction melting furnace under argon protection. The alloy billet is obtained by casting with a graphite mold.

[0049] Hot rolling treatment: The billet is protected at 850℃ for 5 hours and then hot rolled, with a hot rolling deformation of 50%.

[0050] Solution treatment: The hot-rolled alloy was solution treated at 850℃ for 2 hours and then rapidly water-cooled to obtain a supersaturated solid solution;

[0051] Cold rolling: The alloy after solution treatment is cold rolled in multiple passes to achieve a deformation of up to 90%;

[0052] Aging treatment: The cold-rolled alloy was placed in a resistance furnace and aged at 500℃ for 10 hours to obtain Ni3Ti reinforced copper-based in-situ composite material.

[0053] The Ni3Ti-reinforced copper-based in-situ composite material was tested, such as... Figure 2 As shown, from Figure 2 A large number of micron-sized Ni3Ti in-situ reinforcing phases can be observed in the alloy. The excellent mechanical properties of the alloy are attributed to the interaction between the micron-sized Ni3Ti in-situ reinforcing phases and dislocations, while the improved conductivity of the alloy is attributed to the aging precipitation of nano-sized Ni3Ti phases.

[0054] Example 3:

[0055] A method for preparing a Ni3Ti-reinforced copper-based in-situ composite material includes the following steps:

[0056] According to the mass percentage, 3% Ni, 1% Ti, 0.3Sc, and the balance Cu are batched and melted in a vacuum induction melting furnace under argon protection. The alloy billet is obtained by casting with a graphite mold.

[0057] Hot rolling treatment: The billet is protected at 850℃ for 5 hours and then hot rolled, with a hot rolling deformation of 50%.

[0058] Solution treatment: The hot-rolled alloy was solution treated at 850℃ for 3 hours and then rapidly water-cooled to obtain a supersaturated solid solution;

[0059] Cold rolling: The alloy after solution treatment is cold rolled in multiple passes to achieve a deformation of up to 93%;

[0060] Aging treatment: The cold-rolled alloy was placed in a resistance furnace and aged at 500℃ for 8 hours to obtain Ni3Ti reinforced copper-based in-situ composite material.

[0061] The Ni3Ti-reinforced copper-based in-situ composite material was tested, such as... Figure 3 As shown, from Figure 3 A large number of micron-sized Ni3Ti in-situ reinforcing phases can be observed in the alloy. The excellent mechanical properties of the alloy are attributed to the interaction between the micron-sized Ni3Ti in-situ reinforcing phases and dislocations, while the improved conductivity of the alloy is attributed to the aging precipitation of nano-sized Ni3Ti phases.

[0062] Comparative Example 1:

[0063] The difference between Comparative Example 1 and Example 3 is that no Sc element was added in Comparative Example 1, while the rest is the same as Example 3.

[0064] Comparative Example 2:

[0065] The difference between Comparative Example 2 and Example 3 is that the mass percentage of Ni to Ti in Comparative Example 2 is 7:1, while the rest is the same as in Example 3.

[0066] Mechanical properties, electrical conductivity, and softening temperature of Examples 1-3 and Comparative Examples 1-2 were tested, and the results are shown in Table 1 below.

[0067] Table 1:

[0068]

[0069]

[0070] Analysis of the data in Table 1 shows that the Ni3Ti reinforced copper-based in-situ composite material prepared in this application exhibits excellent tensile strength, electrical conductivity, and softening temperature. Specifically, the difference between Comparative Example 1 and Example 3 is that Sc element was not added in Comparative Example 1, while other aspects were the same as in Example 3. It can be seen that the tensile strength and softening temperature in Comparative Example 1 are significantly reduced. The difference between Comparative Example 2 and Example 3 is that the mass percentage of Ni to Ti in Comparative Example 2 is 7:1, but the tensile strength, electrical conductivity, and softening temperature are all significantly reduced. This comprehensively demonstrates that the composition and component ratio of this application have a synergistic effect, which helps to obtain a composite material with significantly improved tensile strength, electrical conductivity, and softening temperature.

[0071] 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.

[0072] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.

Claims

1. A Ni3Ti reinforced copper-based in-situ composite material, characterized in that, The Ni3Ti reinforced copper-based in-situ composite material comprises a micron-sized Ni3Ti reinforcing phase, and by mass percentage, the Ni3Ti reinforced copper-based in-situ composite material comprises the following components: Ni: 2.5~3.5wt%, Ti: 0.8~1.2wt%, auxiliary elements 0.1%~2.0%, and the balance being Cu; The mass percentage of Ni and Ti is (2.8~3.5):1; The auxiliary element is one of Zr, Y and Sc, and by mass percentage, Zr: 0.1~0.8wt%, Y: 0.1~0.6wt%, Sc: 0.1~0.6wt%.

2. A method for preparing a Ni3Ti reinforced copper-based in-situ composite material, characterized in that, The preparation method is used to prepare the Ni3Ti reinforced copper-based in-situ composite material as described in claim 1, and the preparation method includes the following steps: Cu, Ni, Ti and auxiliary elements are added to a vacuum induction furnace, smelted under protective gas conditions, and then cast to obtain an alloy billet. The alloy billet was subjected to hot rolling, solution treatment, multiple cold rolling processes, and aging treatment to obtain Ni3Ti reinforced copper-based in-situ composite material. The hot rolling process is performed at a temperature of 820℃ to 880℃, with a deformation of 40% to 60%; the cold rolling process is performed with a deformation of 80% or more.

3. The preparation method according to claim 2, characterized in that, The solution treatment is performed at a temperature of 850℃ to 950℃ for a duration of 1 hour to 3 hours.

4. The preparation method according to claim 2, characterized in that, The aging treatment is performed at a temperature of 450℃ to 600℃ for a duration of 8 hours to 12 hours.

5. The preparation method according to claim 2, characterized in that, After the solution treatment, the Ni3Ti-reinforced copper-based in-situ composite material is water-quenched, and the micron-sized Ni3Ti in-situ reinforcing phase is dissolved back and precipitated during the subsequent cooling process.

6. The preparation method according to claim 2, characterized in that, After multiple cold rolling processes, the micron-sized Ni3Ti reinforcing phase is uniformly distributed along the deformation zone.

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