阅读说明：本技术 一种双级时效工艺制备CuCrZr合金的方法 (Method for preparing CuCrZr alloy by two-stage aging process ) 是由 田艳中 凌国平 胡敬源 于 2021-10-15 设计创作，主要内容包括：本发明的一种双级时效工艺制备CuCrZr合金的方法,属于合金制备技术领域。步骤为：按质量百分比,Cr 0.3-0.9％,Zr 0.1-0.3％,余量为铜,炼CuCrZr块体合金；块体合金依次经热变形与固溶处理,获得固溶合金；冷却后进行冷轧,获得冷轧后合金；冷轧后合金进行一级时效和二级时效处理,控制一级时效处理温度为100-200℃,制得CuCrZr合金。本发明的CuCrZr合金加工工艺方式简单,相比于单级时效热处理的CuCrZr合金具有提升强度并改善合金的延伸率,在工程应用上具有更大的潜力,对电子万能试验机测得的拉伸曲线进行分析,双级时效后合金强塑积得到明显提升；且导电性能稳步提升。(The invention discloses a method for preparing a CuCrZr alloy by a two-stage aging process, and belongs to the technical field of alloy preparation. The method comprises the following steps: according to the mass percentage, 0.3 to 0.9 percent of Cr, 0.1 to 0.3 percent of Zr and the balance of copper are smelted into CuCrZr bulk alloy; carrying out thermal deformation and solid solution treatment on the block alloy in sequence to obtain a solid solution alloy; cooling and then carrying out cold rolling to obtain a cold-rolled alloy; and performing primary aging treatment and secondary aging treatment on the alloy after cold rolling, and controlling the temperature of the primary aging treatment to be 100-200 ℃ to prepare the CuCrZr alloy. Compared with the single-stage aging heat treatment CuCrZr alloy, the CuCrZr alloy has the advantages that the processing method is simple, the strength is improved, the elongation of the alloy is improved, the potential is higher in engineering application, a tensile curve measured by an electronic universal testing machine is analyzed, and the alloy product of strength and elongation is obviously improved after two-stage aging; and the conductivity is stably improved.)

1. A method for preparing a CuCrZr alloy by a two-stage aging process is characterized by comprising the following steps:

(1) smelting a CuCrZr bulk alloy according to the mass ratio, wherein the CuCrZr bulk alloy comprises the following components in percentage by mass: 0.3 to 0.9 percent of Cr, 0.1 to 0.3 percent of Zr and the balance of copper;

(2) sequentially carrying out thermal deformation and solid solution treatment on the CuCrZr bulk alloy to obtain a solid solution alloy;

(3) after cooling the solid solution alloy, cold rolling to obtain a cold-rolled alloy;

(4) and performing two-stage aging treatment on the alloy after cold rolling to prepare the CuCrZr alloy, wherein the two-stage aging treatment comprises first-stage aging treatment and second-stage aging treatment, and the temperature of the first-stage aging treatment is 100-200 ℃.

2. The method for preparing the CuCrZr alloy by the double-stage aging process according to claim 1, wherein in the step (1), the CuCrZr bulk alloy comprises the following components in percentage by mass: 0.7% of Cr, 0.19% of Zr and the balance of copper.

3. The method for preparing the CuCrZr alloy by the two-stage aging process according to claim 1, wherein in the step (2), the thermal deformation temperature is 700-900 ℃, and the heat preservation time is 1-2h, so as to obtain the thermal deformation alloy; the solid solution treatment is carried out in a muffle furnace, the solid solution temperature is 950-.

4. The method for preparing the CuCrZr alloy by the double-stage aging process according to claim 1, wherein in the step (3), the solid solution alloy cooling mode is water quenching cooling, and the scalping treatment is carried out before cold rolling to remove an oxide layer; the cold rolling single-pass pressure is 10-35%, and the total pressure is 90-97%.

5. The method for preparing the CuCrZr alloy by the double-stage aging process according to claim 1, wherein in the step (4), the first-stage aging is carried out in a salt bath furnace, the second-stage aging is carried out in a muffle furnace, and the alloy after the first-stage aging is cooled by water quenching and then subjected to the second-stage aging.

6. The method for preparing the CuCrZr alloy by the two-stage aging process according to claim 1, wherein in the step (4), the first-stage aging time is 4-6h, the second-stage aging treatment temperature is 385-475 ℃, and the second-stage aging time is 1-2.5 h.

7. The method for preparing CuCrZr alloy by the two-stage aging process as claimed in claim 6, wherein in the step (4), the temperature of the first-stage aging treatment is 120-180 ℃, and the temperature of the second-stage aging treatment is 400-450 ℃.

8. The method for preparing the CuCrZr alloy by the double-stage aging process according to claim 7, wherein in the step (4), the temperature of the first-stage aging treatment is 150 ℃, and the temperature of the second-stage aging treatment is 425 ℃.

9. The method for preparing CuCrZr alloy by the two-stage aging process as claimed in claim 1, wherein in the step (4), the CuCrZr alloy has a strength and elongation of 6534-8760MPa, a tensile strength of 542-603MPa, an elongation of 11-15%, a hardness of 162-199HV0.2, and an electrical conductivity of 77-81% IACS.

10. The method for preparing CuCrZr alloy by the two-stage aging process according to claim 9, wherein in the step (4), the CuCrZr alloy has a product strength and elongation of 6996-8760 MPa%.

The technical field is as follows:

the invention belongs to the technical field of alloy preparation, and particularly relates to a method for preparing a CuCrZr alloy by a two-stage aging process.

Background art:

the CuCrZr alloy has great advantages in the field of high-strength and high-conductivity materials, and the reason is that Cr and Zr elements are fully precipitated due to extremely low solid solubility in a copper matrix in a room temperature environment. The precipitated phase can improve the strength of the alloy, reduce the content of solid solution elements in the alloy and improve the conductivity of the alloy. The alloy is widely applied to the industrial fields of electric power, electronics, machinery and the like, and can be used as an integrated circuit lead frame, a high-power asynchronous traction motor rotor, an electrified railway contact wire, a high-pulse magnetic field conductor material and the like. In 2020, Guangdong Huaxing heat exchange equipment Co., Ltd discloses a CuCrZr alloy and a preparation method thereof (CN109385555B), and the alloy has good comprehensive performance.

The CuCrZr alloy has the advantages of high strength and high conductivity because of the extremely low solid solubility of alloy elements, but because of the limitation of the solid solubility, the strength of the alloy cannot be obviously improved by adding excessive Cr and Zr elements, so the Cr content in the common CuCrZr alloy is less than 1 percent by mass ratio. When the alloy performance is changed by regulating the content of alloy elements, the alloy strength is improved along with the increase of the content of Cr and Zr elements, but the elongation is reduced along with the increase of the content of Zr elements; when the content of the alloy elements is reduced, the plasticity of the alloy is improved, but the strength is too low to be applied in practical environment. In addition, it is difficult to balance the plasticity and the strength even if the amount of deformation is changed, and an increase in one is accompanied by a decrease in the other. In practical applications (such as contact wires), the tensile strength of the alloy is continuously improved with the updating of products. However, the material strengthening effect is evaluated, and the single pursuit of ultimate tensile strength or elongation as much as possible does not meet the practical application standard. The performance of the alloy in the stretching process is difficult to be comprehensively evaluated by taking single tensile strength or elongation as a standard, and at the moment, the evaluation by taking the product of strength and elongation as a standard is particularly important. The CuCrZr alloy prepared by the prior art has most of the product of strength and elongation distributed between 3000 and 5000MPa and is difficult to be further improved.

The invention content is as follows:

the invention aims to overcome the defects in the prior art and provides a method for preparing a CuCrZr alloy by a two-stage aging process.

In order to achieve the purpose, the invention adopts the following technical scheme:

a method for preparing a CuCrZr alloy by a two-stage aging process comprises the following steps:

(1) smelting a CuCrZr bulk alloy according to the mass ratio, wherein the CuCrZr bulk alloy comprises the following components in percentage by mass: 0.3 to 0.9 percent of Cr, 0.1 to 0.3 percent of Zr and the balance of copper;

(2) sequentially carrying out thermal deformation and solid solution treatment on the CuCrZr bulk alloy to obtain a solid solution alloy;

(3) after cooling the solid solution alloy, cold rolling to obtain a cold-rolled alloy;

(4) and performing two-stage aging treatment on the alloy after cold rolling to obtain the CuCrZr alloy, wherein the two-stage aging treatment comprises first-stage aging treatment and second-stage aging treatment, the temperature of the first-stage aging treatment is 100-200 ℃, and the temperature of the second-stage aging treatment is 385-475 ℃.

In the step (1), the smelting operation is carried out in a vacuum induction furnace.

In the step (1), preferably, the CuCrZr bulk alloy comprises the following components in percentage by mass: 0.7% of Cr, 0.19% of ZrC and the balance of copper.

In the step (2), the thermal deformation temperature is 700-900 ℃, and the heat preservation time is 1-2h, so as to obtain a thermal deformation alloy;

in the step (2), the solid solution treatment is carried out in a muffle furnace, the solid solution temperature is 950-;

in the step (3), the cooling mode of the solid solution alloy is water quenching cooling, and the scalping treatment is carried out before cold rolling to remove an oxide layer.

In the step (3), the cold rolling single-pass pressure is 10-35%, and the total pressure is 90-97%.

In the step (4), the primary aging is carried out in a salt bath furnace, and the secondary aging is carried out in a muffle furnace.

In the step (4), the alloy after the first-stage aging is quenched and cooled by water, and then the second-stage aging is carried out.

In the step (4), the primary aging time is 4-6h, and the secondary aging time is 1-2.5 h.

In the step (4), preferably, the temperature of the primary aging treatment is 120-180 ℃.

In the step (4), the temperature of the primary aging treatment is preferably 150 ℃.

In the step (4), preferably, the temperature of the secondary aging treatment is 400-450 ℃.

In the step (4), the temperature of the secondary aging treatment is preferably 425 ℃.

In the step (4), the CuCrZr alloy has a strength-ductility product of 6534-8760MPa, a tensile strength of 542-603MPa, an elongation of 11-15%, a hardness of 162-199HV0.2 and an electrical conductivity of 77-81% IACS.

In the step (4), the strength-plasticity product of the CuCrZr alloy is preferably 6996-8760 MPa%.

In the step (4), the alloy hardness is measured by using a semi-automatic Vickers hardness tester, the tensile strength is measured by using a universal electronic tester to perform a tensile test and analyze a tensile curve, and the conductivity is measured by using a direct current resistance tester.

In the primary aging process of the alloy after cold rolling, a large number of GP zones are uniformly distributed in a matrix in a specific low-temperature environment, conditions are created for the non-uniform nucleation of a second phase, and the free energy of nucleation and growth of the alloy in a high-temperature environment is reduced. The application of the specific two-stage aging avoids the uneven precipitation of the second phase along the grain boundary, is beneficial to the uniform and dense distribution of the second phase, and improves the product of strength and elongation of the alloy.

The invention has the beneficial effects that:

compared with the single-stage aging heat treatment CuCrZr alloy, the CuCrZr alloy has the advantages that the strength is improved, the elongation of the alloy is improved, the CuCrZr alloy has greater potential in engineering application, a tensile curve measured by an electronic universal testing machine is analyzed, and the alloy product of strength and elongation is obviously improved after two-stage aging; the conductivity is measured by using a direct current resistance tester, and the conductivity of the alloy is stably improved after two-stage aging.

The specific implementation mode is as follows:

the present invention will be described in further detail with reference to examples.

Example 1

The alloy adopted by the invention is prepared by a vacuum induction furnace and then is subjected to thermal deformation to obtain a block alloy with the thickness of 30mm, and the composition and the ratio (mass%) are as follows: 0.5 percent of Cr0.13 percent of Zr0.13 percent, and the balance of copper;

(1) solution treatment, keeping the temperature at 960 ℃ for 1h, and quenching;

(2) the processing technology comprises the following steps: cold rolling, namely rolling the block alloy with the thickness of 30mm to 1mm, wherein the reduction is 96%;

(3) first-stage aging heat treatment: keeping the temperature at 150 ℃ for 5h, and quenching;

(4) and (3) secondary aging heat treatment: keeping the temperature at 425 ℃ for 2h, and quenching;

the results of the comprehensive property tests of the test alloy and the comparative alloy after the above-mentioned thermomechanical treatment process are shown in Table 1.

Comparative examples 1 to 1

The difference from example 1 is that the first stage aging process is omitted, and the alloy product is obtained, and the performance indexes are shown in table 1 after detection.

Example 2

The alloy adopted by the invention is prepared by a vacuum induction furnace and then is subjected to thermal deformation to obtain a block alloy with the thickness of 30mm, and the composition and the ratio (mass%) are as follows: 0.5 percent of Cr0.13 percent of Zr0.13 percent, and the balance of copper;

(1) solution treatment, keeping the temperature at 960 ℃ for 1h, and quenching;

(2) the processing technology comprises the following steps: cold rolling, namely rolling the block alloy with the thickness of 30mm to 1mm, wherein the reduction is 96%;

(3) first-stage aging heat treatment: keeping the temperature at 120 ℃ for 5.5h, and quenching;

(4) and (3) secondary aging heat treatment: keeping the temperature at 400 ℃ for 2.5h, and quenching;

the results of the comprehensive property tests of the test alloy and the comparative alloy after the above-mentioned thermomechanical treatment process are shown in Table 1.

Comparative example 2-1

The difference from example 2 is that the first stage aging process is omitted, and the alloy product is obtained, and the performance indexes are shown in table 1 after detection.

Example 3

The alloy adopted by the invention is prepared by a vacuum induction furnace and then is subjected to thermal deformation to obtain a block alloy with the thickness of 30mm, and the composition and the ratio (mass%) are as follows: 0.7 percent of Cr0.19 percent, 0.19 percent of Zr0 percent and the balance of copper;

(1) solution treatment, keeping the temperature at 960 ℃ for 1h, and quenching;

(2) the processing technology comprises the following steps: cold rolling, namely rolling the block alloy with the thickness of 30mm to 1mm, wherein the reduction is 96%;

(3) first-stage aging heat treatment: keeping the temperature at 100 ℃ for 6h, and quenching;

(4) and (3) secondary aging heat treatment: keeping the temperature at 385 ℃ for 3h, and quenching;

the results of the comprehensive property tests of the test alloy and the comparative alloy after the above-mentioned thermomechanical treatment process are shown in Table 1.

Comparative example 3-1

The difference from example 3 is that the first stage aging process is omitted, and the alloy product is obtained, and the performance indexes are shown in table 1 after detection.

Example 4

The alloy adopted by the invention is prepared by a vacuum induction furnace and then is subjected to thermal deformation to obtain a block alloy with the thickness of 30mm, and the composition and the ratio (mass%) are as follows: 0.7 percent of Cr0.19 percent, 0.19 percent of Zr0 percent and the balance of copper;

(1) solution treatment, heat preservation at 950 ℃ for 2h, and quenching;

(2) the processing technology comprises the following steps: cold rolling, namely rolling the block alloy with the thickness of 30mm to 1mm, wherein the reduction is 96%;

(3) first-stage aging heat treatment: keeping the temperature at 120 ℃ for 5.5h, and quenching;

(4) and (3) secondary aging heat treatment: keeping the temperature at 400 ℃ for 2.5h, and quenching;

the results of the comprehensive property tests of the test alloy and the comparative alloy after the above-mentioned thermomechanical treatment process are shown in Table 1.

Comparative example 4-1

The difference from example 4 is that the first stage aging process is omitted, and the alloy product is obtained, and the performance indexes are shown in table 1 after detection.

Example 5

The alloy adopted by the invention is prepared by a vacuum induction furnace and then is subjected to thermal deformation to obtain a block alloy with the thickness of 30mm, and the composition and the ratio (mass%) are as follows: 0.7 percent of Cr0.19 percent, 0.19 percent of Zr0 percent and the balance of copper;

(1) solution treatment, keeping the temperature at 960 ℃ for 1h, and quenching;

(2) the processing technology comprises the following steps: cold rolling, namely rolling the block alloy with the thickness of 30mm to 1mm, wherein the reduction is 96%;

(3) first-stage aging heat treatment: keeping the temperature at 150 ℃ for 5h, and quenching;

(4) and (3) secondary aging heat treatment: keeping the temperature at 425 ℃ for 2h, and quenching;

the results of the comprehensive property tests of the test alloy and the comparative alloy after the above-mentioned thermomechanical treatment process are shown in Table 1.

Comparative example 5-1

The difference from example 5 is that the first stage aging process is omitted, and the alloy product is obtained, and the performance indexes are shown in table 1 after detection.

Comparative examples 5 to 2

The difference from example 5 is that the primary aging temperature is 50 ℃ and the time is 5h, the product of strength and elongation is as low as 6292 after detection, the rest performance data lines are detailed in table 1, and analysis shows that the primary aging temperature is too low, so that only recovery occurs in the alloy matrix, and the atomic diffusion rate is too slow at low temperature and the nucleation rate is too low, so that the product of strength and elongation is obviously reduced.

Comparative examples 5 to 3

The difference from example 5 is that the primary aging temperature is 250 ℃, the time is 5h, the product of strength and elongation is as low as 6852 after detection, and the rest performance data lines are detailed in table 1, and analysis shows that the reason is that the primary aging temperature is too high, annihilation of dislocation is promoted, the nucleation rate of the second phase is reduced, and the product of strength and elongation is remarkably reduced.

Example 6

The alloy adopted by the invention is prepared by a vacuum induction furnace and then is subjected to thermal deformation to obtain a block alloy with the thickness of 30mm, and the composition and the ratio (mass%) are as follows: 0.7 percent of Cr0.19 percent, 0.19 percent of Zr0 percent and the balance of copper;

(1) solution treatment, keeping the temperature at 960 ℃ for 1h, and quenching;

(2) the processing technology comprises the following steps: cold rolling, namely rolling the block alloy with the thickness of 30mm to 1mm, wherein the reduction is 96%;

(3) first-stage aging heat treatment: keeping the temperature at 180 ℃ for 4.5h, and quenching;

(4) and (3) secondary aging heat treatment: keeping the temperature at 450 ℃ for 1.5h, and quenching;

the results of the comprehensive property tests of the test alloy and the comparative alloy after the above-mentioned thermomechanical treatment process are shown in Table 1.

Comparative example 6-1

The difference from example 6 is that the first stage aging process is omitted, and the alloy product is obtained, and the performance indexes are shown in table 1 after detection.

Example 7

The alloy adopted by the invention is prepared by a vacuum induction furnace and then is subjected to thermal deformation to obtain a block alloy with the thickness of 30mm, and the composition and the ratio (mass%) are as follows: 0.7 percent of Cr0.19 percent, 0.19 percent of Zr0 percent and the balance of copper;

(1) solution treatment, keeping the temperature at 960 ℃ for 1h, and quenching;

(2) the processing technology comprises the following steps: cold rolling, namely rolling the block alloy with the thickness of 30mm to 1mm, wherein the reduction is 96%;

(3) first-stage aging heat treatment: keeping the temperature at 200 ℃ for 4h, and quenching;

(4) and (3) secondary aging heat treatment: keeping the temperature at 475 ℃ for 1h, and quenching;

the results of the comprehensive property tests of the test alloy and the comparative alloy after the above-mentioned thermomechanical treatment process are shown in Table 1.

Comparative example 7-1

The difference from example 7 is that the first stage aging process is omitted, and alloy products are obtained, and the performance indexes of the alloy products are shown in table 1 after detection.

Example 8

The alloy adopted by the invention is prepared by a vacuum induction furnace and then is subjected to thermal deformation to obtain a block alloy with the thickness of 30mm, and the composition and the ratio (mass%) are as follows: 0.9 percent of Cr0.24 percent of Zr0.24 percent, and the balance of copper;

(1) solution treatment, keeping the temperature at 960 ℃ for 1h, and quenching;

(2) the processing technology comprises the following steps: cold rolling, namely rolling the block alloy with the thickness of 30mm to 1mm, wherein the reduction is 96%;

(3) first-stage aging heat treatment: keeping the temperature at 150 ℃ for 5h, and quenching;

(4) and (3) secondary aging heat treatment: keeping the temperature at 425 ℃ for 2h, and quenching;

the results of the comprehensive property tests of the test alloy and the comparative alloy after the above-mentioned thermomechanical treatment process are shown in Table 1.

Comparative example 8-1

The difference from example 8 is that the first stage aging process is omitted, and the alloy product is obtained, and the performance indexes are shown in table 1 after detection.

Example 9

The alloy adopted by the invention is prepared by a vacuum induction furnace and then is subjected to thermal deformation to obtain a block alloy with the thickness of 30mm, and the composition and the ratio (mass%) are as follows: 0.9 percent of Cr0.24 percent of Zr0.24 percent, and the balance of copper;

(1) solution treatment, heat preservation at 950 ℃ for 2h, and quenching;

(2) the processing technology comprises the following steps: cold rolling, namely rolling the block alloy with the thickness of 30mm to 1mm, wherein the reduction is 96%;

(3) first-stage aging heat treatment: keeping the temperature at 120 ℃ for 5.5h, and quenching;

(4) and (3) secondary aging heat treatment: keeping the temperature at 400 ℃ for 2.5h, and quenching;

the results of the comprehensive property tests of the test alloy and the comparative alloy after the above-mentioned thermomechanical treatment process are shown in Table 1.

Comparative example 9-1

The difference from example 9 is that the first stage aging process is omitted, and the alloy product is obtained, and the performance indexes are shown in table 1 after detection.

The above examples 1-8 and the comparative preparation process parameters and the overall properties of the prepared alloy products are shown in Table 1 below.

TABLE 1

In the table, D is the meaning of the comparative example, and the unit of heat treatment, solid solution and twice aging is h; the unit of the product of strength and elongation is MPa, the unit of tensile strength is MPa, the unit of elongation is HV0.2, and the unit of conductivity is ACS.