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CN-121976086-A - High-strength high-conductivity C19400 copper-based composite material and preparation method thereof

CN121976086ACN 121976086 ACN121976086 ACN 121976086ACN-121976086-A

Abstract

The application relates to the technical field of copper alloy, in particular to a high-strength high-conductivity C19400 copper-based composite material and a preparation method thereof. The method mainly comprises the steps of mixing copper powder, iron powder, copper-phosphorus alloy, modified nano TiC and copper-cerium alloy powder, performing high-energy ball milling, vacuum drying, compression molding, pressure sintering and double-stage aging treatment to obtain the high-strength high-conductivity C19400 copper-based composite material, wherein the modified nano TiC is coated by a rare earth Ce precursor and subjected to weak oxidation heat treatment to form a cerium oxide film layer on the surface of the modified nano TiC in situ, so that the dispersibility of nano TiC and the interface combination of the nano TiC and a copper matrix can be improved. According to the application, through the collocation of raw materials and preparation steps, the effects of precipitation strengthening, dispersion strengthening and interface strengthening can be effectively coordinated, and the strength, conductivity and tissue stability of the material are improved.

Inventors

  • SONG YU
  • LI TIE
  • WANG YINGXIAN
  • HAO YUXIANG
  • WEN TONGQIANG

Assignees

  • 洛阳职业技术学院

Dates

Publication Date
20260505
Application Date
20260407

Claims (9)

  1. 1. The preparation method of the high-strength high-conductivity C19400 copper-based composite material is characterized by comprising the following steps of: (1) 92-94 parts of copper powder, 2.2-2.5 parts of iron powder, 3.6-4 parts of copper-phosphorus alloy, 0.5-1 part of modified nano TiC and 0.25-0.55 part of copper-cerium alloy powder are mixed according to parts by weight, high-energy ball milling is carried out under the protection of argon, the ball-material ratio is 12-15:1, the rotating speed is 450-500r/min, and the duration is 18-24 hours, so that composite powder is obtained; (2) Drying the composite powder under the condition that the vacuum degree is less than or equal to 0.1Pa, wherein the temperature during drying adopts a staged heating strategy, namely, firstly heating to 50-60 ℃ and keeping for 2-3 hours, and then heating to 80-90 ℃ and keeping for 10-12 hours; (3) Pressing into green body under 250-300MPa, and maintaining the pressure for 1-2min; (4) Adopting hot-pressing sintering, preserving heat and pressure for 45-60min at the temperature of 920-960 ℃ and the pressure of 30MPa, and then introducing argon gas to rapidly cool to room temperature; (5) Sequentially carrying out first-stage aging treatment at 400-420 ℃ and second-stage aging treatment at 450-480 ℃ in a protective atmosphere to obtain a high-strength high-conductivity C19400 copper-based composite material; wherein, the preparation of the modified nano TiC in the step (1) comprises the following steps: S1, carrying out acid washing and impurity removal on nano TiC powder, and dispersing the nano TiC powder in absolute ethyl alcohol by ultrasonic to obtain TiC suspension; s2, adding a precursor solution of rare earth Ce into the TiC suspension, adjusting the pH value to 8-10, stirring and carrying out sol-gel reaction; S3, after drying, carrying out heat treatment for 1-2 hours in a weak oxidizing atmosphere at 400-550 ℃, and forming a cerium oxide film layer on the surface of the nano TiC in situ to obtain the modified nano TiC.
  2. 2. The method for preparing the high-strength and high-conductivity C19400 copper-based composite material according to claim 1, wherein the precursor solution in the step S2 is an ethanol solution of cerium nitrate hexahydrate, and the concentration is 0.05-0.15mol/L.
  3. 3. The method for preparing the high-strength and high-conductivity C19400 copper-based composite material according to claim 1, wherein in the step S3, the weak oxidizing atmosphere is an argon-oxygen mixture with an oxygen content of 0.5% -1% by volume.
  4. 4. The preparation method of the high-strength high-conductivity C19400 copper-based composite material, according to claim 1, is characterized in that the weight percentage of phosphorus in the copper-phosphorus alloy in the step (1) is 5% -10%, and the weight percentage of cerium in the copper-cerium alloy powder in the step (1) is 18% -22%.
  5. 5. The method for preparing the high-strength and high-conductivity C19400 copper-based composite material according to claim 1, wherein an average particle size of nano TiC in the step S1 is 50-100nm, an average particle size of iron powder in the step (1) is 1-5 μm, and an average particle size of copper powder in the step (1) is 10-30 μm.
  6. 6. The method for preparing the high-strength and high-conductivity C19400 copper-based composite material according to claim 1, wherein in the step (1), the ball milling process is stopped for 10-15min every 2-3h to prevent heat accumulation, and stearic acid accounting for 0.5% -1.0% of the total weight of the powder is added as an auxiliary agent in the ball milling process.
  7. 7. The method for preparing a high-strength and high-conductivity C19400 copper-based composite according to claim 1, wherein in step (4), a cooling rate of said rapid cooling is not lower than 50 ℃.
  8. 8. The method for preparing the high-strength high-conductivity C19400 copper-based composite material according to claim 1, wherein in the step (5), the time of the aging treatment in the first stage is 1-2h, the time of the aging treatment in the second stage is 2-3h, and the temperature rising rate between the first stage and the second stage is controlled to be 2-3 ℃ per minute.
  9. 9. The high-strength high-conductivity C19400 copper-based composite material prepared by the method according to any one of claims 1 to 8, which is characterized by comprising a copper matrix, tiC particles dispersed in the copper matrix and Fe 3 P phase, wherein the surfaces of the TiC particles are provided with cerium dioxide film layers, and the tensile strength of the composite material is more than or equal to 670MPa, the conductivity is more than or equal to 80% IACS, and the softening temperature is more than or equal to 570 ℃.

Description

High-strength high-conductivity C19400 copper-based composite material and preparation method thereof Technical Field The application relates to the technical field of copper alloy, in particular to a high-strength high-conductivity C19400 copper-based composite material and a preparation method thereof. Background The C19400 copper alloy belongs to typical high-strength high-conductivity copper-iron-phosphorus alloy, and is widely applied to the fields of integrated circuit lead frames, electronic connectors, precise conductive structural members, high-reliability electronic packaging materials and the like because of the high conductivity, good strength, heat resistance and molding processability. With the rapid development of electronic information industry, automotive electronics and high-power devices, related components put higher demands on copper-based materials, not only are materials required to have higher conductivity, but also materials are required to have higher strength, thermal stability and tissue uniformity in complex service environments. Therefore, how to further improve the strength and the comprehensive service performance of the C19400 copper-based material on the basis of ensuring the conductivity has become an important research direction in the field. The traditional C19400 alloy is mostly prepared by adopting a smelting casting process, but Fe and P are easy to macrosegregation in a large-scale smelting casting process, and due to the limitation of cooling rate, the precipitated Fe 3 P phase is often in a thick needle shape or a thick flake shape, so that the strengthening effect is limited, and the anisotropy of the material is caused. As disclosed in the patent document of publication No. CN120485585A, a method for preparing a high-strength and high-conductivity iron bronze alloy by adopting a casting process is disclosed, by controlling the content of P and reducing the size of the Fe-rich phase and the spacing between the Fe-rich phases, the tensile strength of the prepared iron bronze alloy reaches 600MPa, and the conductivity reaches 70% iacs, but it is very difficult to further improve the performance due to the limitations of the preparation method and the raw materials. In order to overcome the problems of coarse grains and segregation in the smelting process, the powder metallurgy process is becoming an important means for preparing high-performance copper-based composite materials. Ceramic particles are introduced into the copper-based composite material through a powder metallurgy technology, so that the high-temperature softening resistance and yield strength of the material can be remarkably improved, and the defect that the traditional C19400 copper alloy mainly depends on a Fe 3 P phase precipitation strengthening mechanism is overcome. According to the patent document with the publication number of CN119876683A, tiC and ZrC are added into a copper matrix to obtain a copper-based composite material, the copper-based composite material is prepared by a powder metallurgy method, the growth of crystal grains is controlled by controlling sintering time, sintering pressure, sintering temperature, atmosphere and the like, so that the mechanical property of the copper-based composite material is improved, but the copper-based composite material is different from C19400 copper-based material, the components and the properties of the copper-based composite material are greatly different, and the application fields are different. In fact, there is still a major technical hurdle in the existing techniques for powder metallurgy to make C19400 copper-based composites. For example, the simple introduction of a ceramic phase can improve the strength, but the additional hard particles are often poorly combined with a matrix, and the electron scattering cross section is seriously increased, so that the conductivity of the composite material is sharply reduced, and the conventional sintering process lacks control means for the morphology and distribution of the precipitated phase, so that the endogenous Fe 3 P phase and the additional nano reinforcing phase cannot form an effective cooperative pinning effect, and the contradiction between the high strength and the high conductivity of the material is always caused. Based on the above-mentioned drawbacks of the prior art, a new C19400 copper-based composite material that can achieve both strength and electrical conductivity is needed. Disclosure of Invention The application aims at overcoming at least one of the defects in the prior art, provides a high-strength high-conductivity C19400 copper-based composite material and a preparation method thereof, and introduces modified nano TiC and copper-cerium alloy powder into a C19400 copper-based system through the matching of raw materials and preparation steps, and combines high-energy ball milling, vacuum drying, compression molding, pressure sintering and double-stage aging treatment