CN117802428A - Methods to improve copper etching accuracy by using grain orientation - Google Patents

Abstract

The invention discloses a method for improving the etching accuracy of copper materials by utilizing grain orientation. By controlling the recrystallized grain orientation of the copper block to be in a random texture state, or the deformation-aging state of the copper strip, the Brass orientation texture, the S orientation texture, the R orientation texture and the Copper orientation texture coexist. Etching accuracy of copper strip.

Description

Methods to improve copper etching accuracy by using grain orientation

Technical field

The invention relates to the technical field of non-ferrous metal processing, and specifically relates to a method for improving the etching accuracy of copper materials by utilizing grain orientation.

Background technique

With the rapid development of microelectronics, mobile phones, home appliances, automobiles, medical and process decoration, higher requirements have been placed on the etching performance of copper materials, especially for etching lead frames, VCM motors, vapor chambers and other products. Accuracy places extremely high demands. The most commonly used etching materials include iron-phosphorus copper, nickel silicon copper, and chromium (zirconium) copper for lead frames, beryllium copper, titanium copper, nickel-tin copper, etc. for camera VCM motor shrapnel, and stainless steel for vapor chambers. Oxygen copper, red copper, tin-phosphorus bronze, etc., yellow hole, white copper, etc. used for decoration. In these application fields, lead frame products have the highest etching accuracy requirements, with etching spacing as small as 0.03mm to ensure the etching of high-density leads. This type of copper material currently produced cannot meet this demand.

Currently, the commonly used means to improve etching accuracy focus on etching liquids (such as CN112831784A) and their spray forms (such as CN211907390U and CN216585219U). Although this can improve etching accuracy to a certain extent, the characteristics of the etching material itself are also important to the etching accuracy. Impact; Controlling the size of the second phase of copper (such as CN109072341B and CN102286675B) can improve etching accuracy, but it is not enough to improve the size and distribution of the second phase of copper alone. The coordinated control of the orientation distribution and grain size of grains can improve copper Material etching accuracy also has an important impact. JP2021110038A proposes to control EBSD specific crystal orientation, KAM value, average copper grain diameter and second phase size to improve etching performance for Cu-Ni-Si-Co alloys, but this application is only for a single alloy and the strip thickness is <0.3 mm.

Contents of the invention

In view of the shortcomings of the above-mentioned prior art, the present invention, based on the summary and analysis of a large number of experiments, provides a method for improving the etching accuracy of copper materials by utilizing grain orientation for precipitation-strengthened copper materials of different thicknesses, which is specifically reflected in reducing the roughness of the etching surface and improving the etching rate, so that the product has good electrical conductivity, mechanical properties and etching performance.

In order to achieve the above objects, the present invention provides the following technical solutions:

A method of using grain orientation to improve the etching accuracy of copper materials. For copper blocks with a finished thickness of ≥1.5mm, the method includes cold-rolling the copper alloy block/ingot C1 and then performing a short-term high-temperature solid solution S1 to make the copper The average grain size of the block is greatly reduced, and then the aging treatment A1 is performed to achieve the sum of the proportions of Cube orientation texture, S orientation texture, R orientation texture and Copper orientation texture of the grains in the copper block < 30%, forming a copper block with a mainly randomly oriented texture. The surface roughness after etching is <0.5μm, which improves the etching accuracy of the copper block. For copper strips with a thickness of <1.5mm, the method includes passing the copper strip through After the cold rolling deformation C1, a short-term high-temperature solid solution S2 is carried out to greatly reduce the average grain size of the copper strip. Then the cold rolling deformation C2 is carried out, the aging treatment A2 is carried out, and finally the final rolling C3 and the stress relief treatment A3 are carried out to make the copper strip The sum of the proportions of Brass orientation texture, S orientation texture, R orientation texture and Copper orientation texture in the material is >50%, and the proportion of Brass orientation texture is >10%, making the surface of the copper strip rough after etching The thickness is less than 0.4μm, which improves the etching accuracy of copper strips.

Furthermore, the deformation amount of cold rolling deformation C1 is >85%, and the more preferred cold deformation amount is >95%.

Further, the temperature of short-term high-temperature solid solution S1 is >900°C, and the holding time is <10 min. The more preferred solid solution temperature is >950°C, and the holding time is <5 min, so that the average grain size is <10 μm; the short-term high-temperature solid solution S2 is Temperature > 900°C, holding time < 5 min. The more preferred solid solution temperature is > 950°C, holding time < 2 min, so that the average grain size is ≤ 5 μm.

Further, the aging treatment A1 and the aging treatment A2 are maintained at 300℃~550℃ for 2h~10h, and the size of the precipitated phase after aging meets d _max ≤0.5μm.

Furthermore, the deformation amount of cold rolling deformation C2 is ≤70%, and the more preferred cold deformation amount is 40-60%.

Further, the deformation amount of final rolling C3 is ≤40%, and the stress relief treatment A3 is to perform tension annealing and tension bending and straightening treatment on the copper strip. The process is to perform tension annealing at 300-400°C for 30-80 seconds. After annealing The strip is stretched, bent and straightened.

Compared with the existing technology, the present invention provides a method for improving the etching precision of copper materials by controlling the grain orientation of precipitation-strengthened copper materials of different thicknesses, improving the roughness of the etching surface, increasing the etching rate and etching precision, and making the etching precision more precise. The product takes into account good electrical conductivity, mechanical properties and etching performance. For copper blocks with finished thickness ≥1.5mm, the copper blocks should be cold-rolled and deformed with >85% deformation and then subjected to solid solution treatment at >900°C, more preferably at >950°C for <10 minutes, to increase the amount of copper. The bulk recrystallization nucleation rate and accelerated recrystallization nucleation, the grains do not coarsen under short-term solid solution conditions, and the average grain size is maintained <10 μm. At the same time, under sufficient solid solution conditions, the uniform precipitate phase can be achieved Fine and diffusely distributed, the recrystallized grain orientation is mainly random texture, and the sum of the grain Cube orientation texture, S orientation texture, R orientation texture and Copper orientation texture is less than 30%. For copper strips with thickness less than 1.5mm, because the thickness requires multiple cold rolling deformations, the amount of cold rolling deformation is increased before solid solution, and the average grain size is ≤5μm through short-term solution, supplemented by ≤70% cold rolling. The amount of rolling deformation makes the grains elongate along the rolling direction and increases the Brass orientation of the grains. Brass, S, R and Copper textures coexist in the copper strip. Brass orientation texture, S orientation texture, R orientation The sum of the proportion of texture and Copper orientation texture is >50%, and the proportion of Brass orientation texture is >10%. The coexistence of Brass orientation texture, S orientation texture, R orientation texture and Copper orientation texture, where the recrystallized grain orientation is in a random texture state or deformation aging state, all contribute to the reduction and improvement of etching surface roughness. Etching precision, the final surface roughness of the copper block and copper strip after etching is <0.5μm and <0.4μm respectively.

Description of drawings

The description and drawings that constitute a part of this application are used to provide a further understanding of the present invention. The illustrative embodiments of the present invention and their descriptions are used to explain the present invention and do not constitute an improper limitation of the present invention. In the attached picture:

Figure 1 shows a schematic diagram of the preparation process route of the copper material of the present invention;

Figure 2 shows the morphology after etching, the grain size and orientation distribution measured by EBSD of Example 1; Figure (a) in Figure 2 shows the morphology after etching; Figure (b) shows Its EBSD measured grain size distribution diagram; Figure (c) shows its IPF diagram; Figure (d) shows its orientation distribution diagram;

Figure 3 shows the morphology after etching, the grain size and orientation distribution measured by EBSD of Example 2; Figure (a) in Figure 3 shows the morphology after etching; Figure (b) shows the morphology after etching. Its EBSD measured grain size distribution diagram; Figure (c) shows its IPF diagram; Figure (d) shows its orientation distribution diagram;

FIG4 shows the morphology after etching, the grain size and orientation distribution diagram measured by EBSD of Example 3; wherein, FIG4 (a) shows the morphology after etching; FIG4 (b) shows the grain size distribution diagram measured by EBSD; FIG4 (c) shows the IPF diagram; and FIG4 (d) shows the orientation distribution diagram;

Figure 5 shows the morphology after etching, the grain size and orientation distribution measured by EBSD of Example 4; Figure (a) in Figure 5 shows the morphology after etching; Figure (b) shows Its EBSD measured grain size distribution diagram; Figure (c) shows its IPF diagram; Figure (d) shows its orientation distribution diagram;

Figure 6 shows the morphology after etching, the grain size and orientation distribution measured by EBSD of Example 5; Figure (a) in Figure 6 shows the morphology after etching; Figure (b) shows the morphology after etching. Its EBSD measured grain size distribution diagram; Figure (c) shows its IPF diagram; Figure (d) shows its orientation distribution diagram;

Figure 7 shows the morphology after etching, the grain size and orientation distribution measured by EBSD of Example 6; Figure (a) in Figure 7 shows the morphology after etching; Figure (b) shows Its EBSD measured grain size distribution diagram; Figure (c) shows its IPF diagram; Figure (d) shows its orientation distribution diagram;

FIG8 shows the morphology after etching, the grain size and orientation distribution diagram of Example 7 measured by EBSD; wherein FIG8 (a) shows the morphology after etching; FIG8 (b) shows the grain size distribution diagram measured by EBSD; FIG8 (c) shows the IPF diagram; and FIG8 (d) shows the orientation distribution diagram;

Figure 9 shows the morphology after etching, the grain size and orientation distribution measured by EBSD of Comparative Example 1; Figure (a) in Figure 9 shows the morphology after etching; Figure (b) shows Its EBSD measured grain size distribution diagram; Figure (c) shows its IPF diagram; Figure (d) shows its orientation distribution diagram;

Figure 10 shows the morphology after etching, the grain size and orientation distribution measured by EBSD of Comparative Example 2; Figure (a) in Figure 10 shows the morphology after etching; Figure (b) shows Its EBSD measured grain size distribution diagram; Figure (c) shows its IPF diagram; Figure (d) shows its orientation distribution diagram;

Figure 11 shows the post-etching morphology, EBSD-measured grain size and orientation distribution diagram of Comparative Example 3; wherein, Figure 11 (a) shows its post-etching morphology; Figure (b) shows its EBSD-measured grain size distribution diagram; Figure (c) shows its IPF diagram; and Figure (d) shows its orientation distribution diagram.

The morphology after etching refers to the morphology of the surface after full or half etching of the sample. Its surface roughness can reflect the etching accuracy, and the present invention uses Sa to characterize it; BSD determines the grain and size, mainly characterizes the grain morphology and grain size distribution of the material itself, and calculates the average grain size to characterize the size of the grain size; EBSD determines the texture distribution, mainly characterizes the texture type of the matrix in the longitudinal section, and its content and distribution affect the etching morphology. Examples 1-3 are blocks of three different alloys, and Examples 4-7 are strips of four alloys.

Detailed ways

It should be noted that, in the absence of conflict, the embodiments and features in the embodiments of the present application can be combined with each other. The present invention will be described in detail below with reference to the accompanying drawings and in combination with the embodiments.

As described in the background of the present invention, products such as lead frames have high requirements for etching accuracy, and the etching spacing is as small as 0.03mm to ensure the etching of high-density leads. The requirements for the roughness of the copper etching surface are getting higher and higher. The etching accuracy can be improved to a certain extent by improving the etching spray method and etching liquid, but the etching performance can also be improved by regulating the specific crystal orientation of the etching material, the average grain diameter of the copper material and the secondary size. The present invention provides a method for improving the etching accuracy of copper materials of different thicknesses that meet the requirements of various alloys. The copper material grain size and orientation are regulated by processing and heat treatment to improve the roughness of the etching surface, improve the etching rate and etching accuracy, and make the product have good conductivity, mechanical properties and etching performance.

It has been confirmed by the inventor of the present application that by controlling the recrystallized grain size of the copper material to <10 μm and making the orientation consistent, the sum of the proportions of the grain Cube orientation texture, S orientation texture, R orientation texture and Copper orientation texture is < 30%, or the average grain size of the copper material in the deformation aging state is controlled to be less than 5 μm and the Brass orientation of the grains is increased. The proportion of Brass orientation texture, S orientation texture, R orientation texture and Copper orientation texture in the strip The sum of the ratios is >50%, which helps to reduce the roughness of the etched surface and improve the accuracy of the etched product. The specific implementation is as follows:

For blocks with thickness ≥1.5mm:

The copper alloy block/ingot is cold-rolled and deformed C1 and then subjected to short-term high-temperature solid solution S1 to greatly reduce the average grain size of the alloy block, and then is subjected to aging treatment A1 to make the Cube orientation texture of the grains in the alloy block The sum of the proportions of S-oriented texture, S-oriented texture, R-oriented texture and Copper-oriented texture is less than 30%, making the surface roughness of the copper block after etching less than 0.5μm, greatly improving the etching accuracy of the copper block.

Specifically, the copper alloy block is subjected to cold rolling deformation C1, with a deformation amount of >85%, and a more preferred cold rolling deformation amount is >95%.

Specifically, the temperature of the short-term high-temperature solid solution S1 is >900°C, and the holding time is <10 min. The more preferred solid solution temperature is >950°C, and the holding time is <5 min, so that the average grain size is <10 μm;

Specifically, the aging treatment A1 is to maintain the temperature at 300°C to 550°C for 2h to 10h, and the size of the precipitated phase after aging satisfies d _max ≤ 0.5 μm.

For copper alloy strips with thickness <1.5mm:

After the copper alloy strip is cold-rolled and deformed C1, it is subjected to short-term high-temperature solid solution S2 to greatly reduce the average grain size of the alloy strip. It is then subjected to cold-rolled deformation C2, aging treatment A2, and finally final rolling C3 and stress relief. Process A3 so that the sum of the proportions of Brass orientation texture, S orientation texture, R orientation texture and Copper orientation texture in the alloy strip is >50%, and the proportion of Brass orientation texture is >10%, so that copper The surface roughness after etching is less than 0.4μm, which greatly improves the etching accuracy of copper strips.

Specifically, the deformation amount of the cold rolling deformation C1 of the copper alloy strip is >85%, and the more preferred cold rolling deformation amount is >95%.

Specifically, the temperature of short-term high-temperature solid solution S2 is >900°C, and the holding time is <5 min. The more preferred solid solution temperature is >950°C, and the holding time is <2 min, so that the average grain size is <5 μm.

Specifically, the aging treatment A2 is to maintain the temperature at 300°C to 550°C for 2h to 10h, and the size of the precipitated phase after aging satisfies d _max ≤ 0.5 μm.

Specifically, the deformation amount of cold rolling deformation C2 is ≤70%, and the more preferred cold rolling deformation amount is 40-60%. The deformation amount of final rolling C3 is ≤40%. The stress relief treatment A3 is to perform tension annealing and tension bending and straightening treatment on the copper strip. The process is to perform tension annealing at 300-400°C for 30-80 seconds. The annealed strip Perform bending and straightening.

Method for determining grain orientation: Select cast solid solution longitudinal and finished longitudinal section samples according to test requirements for EBSD (electron backscatter diffraction) determination. Use EBSD data analysis software. In the determination area, the orientation difference of each crystal is within 10°, and the proportion of crystal orientation is calculated.

The method of measuring the average grain size (d _ave ): According to the test requirements, select the longitudinal cross-section samples of the cast solid solution state and the finished product state for EBSD (electron backscatter diffraction) measurement, and select the appropriate test area and step for each state. Long, the boundary with an orientation difference of more than 15° is regarded as the statistical average grain size of the grain boundary.

Statistical method for the maximum size of precipitation (d _max ): Select the longitudinal section sample of the aging state according to the test requirements, prepare the sample by polishing and etching to show the precipitation phase of the matrix, select a reasonable field of view under SEM (scanning electron microscope) to measure the size of the precipitation phase.

Measurement of the roughness Sa of the fully etched or semi-etched surface: Use a 10mm×10mm etching window to perform full etching or semi-etching, and observe the roughness of the etched surface. Select the etched surface sample prepared by etching, clean the surface with alcohol, test the surface morphology in a laser/optical confocal profilometer, calculate the surface roughness Sa based on ISO 25178, and test more than three fields of view to calculate the average value of Sa.

The etching rate was calculated by weight loss method, and the calculation formula is as follows: V = 10 ⁴ × △m/(A•ρ•t), where V is etching rate (μm/min), △m is etching mass (mg), A is etching area (cm ² ), ρ is copper density (8.96 g/cm ³ ), and t is etching time (min).

The present invention will be described in detail below with reference to the examples. Examples 1-3 are blocks, and a block preparation process is used. Examples 4-7 are strips, and a strip preparation process is used. The preparation process flow chart is shown in the figure. 1.

Example 1

The components and contents of the copper alloy block in this embodiment are shown in Table 1, the main preparation parameters are shown in Table 2, the properties of the obtained high-performance copper alloy block are shown in Table 3, and the implementation results are shown in Figure 2. The specific preparation process is as follows:

The CuFeP alloy block with a thickness of 20 mm was subjected to 90% cold rolling deformation C1 to obtain a block with a thickness of 2 mm, and then a short-time high-temperature solid solution S1 was carried out. The solid solution process was 950℃ for 8 minutes and then water quenching, so that the average grain size of the alloy block was greatly reduced to 7.48μm. The block after solid solution was subjected to aging treatment A1, and the treatment process was 480℃ for 2h. After aging, the sum of the Cube orientation texture, S orientation texture, R orientation texture and Copper orientation texture of the grains in the alloy block was measured to be 25.9% (＜30%), and the size of the aging precipitation phase met d _max ≤0.5μm. The obtained block was etched, and the surface roughness of the copper block after etching was 0.32μm, and the etching rate reached 35μm/min.

Example 2

The composition and content of the copper alloy block in this embodiment are shown in Table 1, the main preparation parameters are shown in Table 2, the properties of the high-performance copper alloy block product are shown in Table 3, and the implementation results are shown in Figure 3. The specific preparation process is as follows:

The CuNiSi alloy block with a thickness of 20mm is subjected to 92% cold rolling deformation C1 to obtain a block with a thickness of 1.6mm, and then a short-term high-temperature solid solution S1 is performed. The solid solution process is 920°C for 2 minutes and then water quenching to make the alloy block The average grain size is greatly reduced to 4.12 μm. The solid solution block is subjected to aging treatment A1. The treatment process is 450°C for 8 hours. After aging, the Cube orientation texture and S orientation texture of the grains in the alloy block are measured. The total proportion of the texture, R-oriented texture and Copper-oriented texture is 24.7% (<30%), and the size of the aging precipitate phase satisfies d _max ≤0.5μm. The obtained block was etched. The surface roughness of the copper block after etching was 0.20 μm, and the etching rate reached 45 μm/min.

Example 3

The composition and content of the copper alloy block in this embodiment are shown in Table 1, the main preparation parameters are shown in Table 2, the properties of the obtained high-performance copper alloy strip are shown in Table 3, and the implementation results are shown in Figure 4. The specific preparation process is as follows:

The CuCrZrSnZn alloy block with a thickness of 40mm is subjected to 96% cold rolling deformation C1 to obtain a block with a thickness of 1.6mm, and then a short-term high-temperature solid solution S1 is performed. The solid solution process is 980°C for 5 minutes and then water quenching to make the alloy block The average grain size is greatly reduced to 7.37 μm. The solid solution block is subjected to aging treatment A1. The treatment process is 480°C for 4 hours. After aging, the Cube orientation texture and S orientation texture of the grains in the alloy block are measured. The total proportion of the texture, R-oriented texture and Copper-oriented texture is 21.1% (<30%), and the size of the aging precipitate phase satisfies d _max ≤0.5μm. The obtained block was etched. The surface roughness of the copper block after etching was 0.35 μm, and the etching rate reached 30.8 μm/min.

Example 4

The difference between this embodiment and embodiment 1 is that this embodiment is a CuFeP alloy strip, and a strip preparation process is adopted. The composition and content of the copper alloy strip of this embodiment are shown in Table 1, the main preparation parameters are shown in Table 2, the properties of the high-performance copper alloy strip product obtained are shown in Table 3, and the implementation results are shown in Figure 5. The specific preparation process is as follows:

The CuFeP alloy hot-rolled strip with a thickness of 16mm is subjected to 92% cold rolling deformation C1 to obtain a strip with a thickness of 1.28mm. A short-term high-temperature solution S2 is performed. The solution process is 900°C for 4 minutes and then water quenching to make the alloy The average grain size of the block is greatly reduced to 5 μm; then cold rolling deformation C2 is carried out, the cold rolling deformation amount is 45%, and a strip with a thickness of 0.7mm is obtained; then aging treatment A2 is carried out, and the treatment process is 550°C for 8 hours. After final rolling C3 with 40% deformation, a 0.4mm strip was obtained, and then subjected to stress relief treatment A3 held at 300°C for 80 seconds. After tension, bending and straightening, the Brass orientation texture and S orientation texture of the grains in the alloy block were measured. The sum of the proportions of the texture, R-oriented texture and Copper-oriented texture is 73.7%, of which the Brass orientation texture accounts for 16.9%, the average strip grain size is 4.95μm, and the size of the precipitated phase satisfies d _max ≤0.5μm . The obtained copper strip was etched, and the surface roughness after etching was 0.5 μm, and the etching rate reached 28.5 μm/min.

Example 5

The components and contents of the copper alloy strip in this embodiment are shown in Table 1, the main preparation parameters are shown in Table 2, the properties of the high-performance copper alloy strip obtained are shown in Table 3, and the implementation results are shown in Figure 6. The specific preparation process is as follows:

The CuNiSi alloy hot-rolled strip with a thickness of 10mm is subjected to 88% cold rolling deformation C1 to obtain a strip with a thickness of 1.2mm. A short-term high-temperature solution S2 is performed. The solution process is 920°C for 2 minutes and then water quenching to make the alloy The average grain size of the block is greatly reduced to 2.5μm; then cold rolling deformation C2 is carried out, the cold rolling deformation amount is 60%, and a strip with a thickness of 0.48mm is obtained; then aging treatment A2 is carried out, and the treatment process is 450°C for 10 hours , and then after final rolling C3 with 40% deformation, a 0.3mm strip was obtained, which was subjected to stress relief treatment A3 at 350°C for 60 seconds. After tension-bending and straightening, the Brass orientation texture and S-orientation texture of the grains in the alloy block were measured. The sum of the proportions of the texture, R-oriented texture and Copper-oriented texture is 74.6%, of which the Brass orientation texture accounts for 39.1%, the average strip grain size is 1.31μm, and the precipitate phase size satisfies d _max ≤0.5μm . The obtained copper strip was etched, and the surface roughness after etching was 0.16 μm, and the etching rate reached 31 μm/min.

Example 6

The components and contents of the copper alloy strip in this embodiment are shown in Table 1, the main preparation parameters are shown in Table 2, the properties of the high-performance copper alloy strip obtained are shown in Table 3, and the implementation results are shown in Figure 7. The specific preparation process is as follows:

The hot-rolled CuNiP alloy with a thickness of 16 mm was subjected to 95% cold rolling deformation C1 to obtain a strip with a thickness of 0.8 mm, and then subjected to short-time high-temperature solid solution S2. The solid solution process was 920℃ for 1.5 min and then water quenching, so that the average grain size of the alloy block was greatly reduced to 4.3μm; then cold rolling deformation C2 was performed, and the cold rolling deformation was 70%, and a strip with a thickness of 0.24 mm was obtained; then aging treatment A2 was performed, and the treatment process was 380℃ for 10h, and then after final rolling C3 with a deformation of 20%, a 0.2mm strip was obtained, and stress relief treatment A3 was performed at 350℃ for 40s. After stretching and straightening, the total proportion of Brass orientation texture, S orientation texture, R orientation texture and Copper orientation texture in the grains in the alloy block was determined to be 55.8%, of which Brass orientation texture accounted for 15%, the average grain size of the strip was 4.17μm, and the size of the precipitated phase satisfied d _max ≤0.5μm. The obtained copper strip was etched, and the surface roughness after etching was 0. μm, and the etching rate reached 35 μm/min.

Example 7

The composition and content of the copper alloy strip of this embodiment are shown in Table 1, the main preparation parameters are shown in Table 2, the properties of the high-performance copper alloy strip product obtained are shown in Table 3, and the implementation results are shown in Figure 8. The specific preparation process is as follows:

The CuCrZrSnZn alloy hot-rolled strip with a thickness of 16mm is subjected to 93% cold rolling deformation C1 to obtain a strip with a thickness of 1.12mm. A short-term high-temperature solution S2 is performed. The solution process is 980°C for 1 minute and then water quenching to make the alloy The average grain size of the block is greatly reduced to 4.95μm; then cold rolling deformation C2 is carried out, the cold rolling deformation amount is 55%, and a strip with a thickness of 0.5mm is obtained; then aging treatment A2 is carried out, and the treatment process is 480°C for 6 hours , and then after final rolling C3 with 20% deformation, a 0.38mm strip was obtained, which was subjected to stress relief treatment A3 at 400°C for 60S. After tension-bending and straightening, the Brass orientation texture and S-orientation texture of the grains in the alloy block were measured. The sum of the proportions of the texture, R-oriented texture and Copper-oriented texture is 63.3%, of which the Brass orientation texture accounts for 23.6%, the average strip grain size is 4.86μm, and the precipitate phase size satisfies d _max ≤0.5μm . The obtained copper strip was etched, and the surface roughness after etching was 0.35 μm, and the etching rate reached 27 μm/min.

Compared with the embodiment, the solid solution time in the comparative alloy composition is longer, and the grains coarsen and grow after solid solution. The composition and content of the copper alloy block/strip of the comparative example are shown in Table 1. The grain orientation ratio prepared in the comparative example is also inconsistent with the conditions of the present invention. The coarsening process leads to coarse precipitation phases. The main preparation parameters are shown in Table 2, and the etching performance of the obtained copper product is shown in Table 3.

Comparative Example 1

The components and contents of the copper alloy block in this embodiment are shown in Table 1, the main preparation parameters are shown in Table 2, the properties of the obtained high-performance copper alloy block are shown in Table 3, and the implementation results are shown in Figure 9. The specific preparation process is as follows:

The CuFeP alloy block with a thickness of 10mm is subjected to 50% cold rolling deformation C1 to obtain a block with a thickness of 5mm, and then a short-term high-temperature solid solution S1 is performed. The solid solution process is 900°C for 30 minutes and then water quenching to make the alloy block The average grain size was greatly reduced to 45 μm. The solid solution block was subjected to aging treatment A1. The treatment process was 480°C for 2 hours. After aging, the grain Cube orientation texture, S orientation texture, and R of the alloy block were measured. The total proportion of oriented texture and Copper oriented texture is 50.6%. The obtained block was etched. The surface roughness of the copper block after etching was 0.81 μm, and the etching rate reached 18.6 μm/min.

Comparative example 2

The components and contents of the copper alloy strip in this embodiment are shown in Table 1, the main preparation parameters are shown in Table 2, the properties of the high-performance copper alloy strip obtained are shown in Table 3, and the implementation results are shown in Figure 10. The specific preparation process is as follows:

The CuNiSi alloy hot-rolled strip with a thickness of 10mm is subjected to 92% cold rolling deformation C1 to obtain a strip with a thickness of 0.8mm. A short-term high-temperature solution S2 is performed. The solution process is 920°C for 30 minutes and then water quenching to make the alloy The average grain size of the block is greatly reduced to 68 μm; then cold rolling deformation C2 is carried out, the cold rolling deformation amount is 60%, and a strip with a thickness of 0.32mm is obtained; then aging treatment A2 is carried out, and the treatment process is 450°C for 10 hours. After final rolling C3 with 35% deformation, a 0.2mm strip was obtained, which was subjected to stress relief treatment A3 with a 350°C heat preservation for 60S. After tension-bending and straightening, the grain Brass orientation texture, S-orientation texture, and The sum of the proportions of the R-oriented texture and the Copper-oriented texture is 40.9%, of which the Brass-oriented texture accounts for 5.4%, and the average grain size of the strip is 20.22 μm. The obtained copper strip was etched, and the surface roughness after etching was 0.66 μm, and the etching rate reached 21.7 μm/min.

Comparative example 3

The components and contents of the copper alloy strip in this embodiment are shown in Table 1, the main preparation parameters are shown in Table 2, the properties of the high-performance copper alloy strip obtained are shown in Table 3, and the implementation results are shown in Figure 11. The specific preparation process is as follows:

The CuCrZrSnZn alloy hot-rolled strip with a thickness of 5mm is subjected to 75% cold rolling deformation C1 to obtain a strip with a thickness of 1.25mm. A short-term high-temperature solution S2 is performed. The solution process is 980°C for 30 minutes and then water quenching to make the alloy The average grain size of the block is greatly reduced to 46 μm; then cold rolling deformation C2 is carried out, the cold rolling deformation amount is 50%, and a strip with a thickness of 0.6mm is obtained; then aging treatment A2 is carried out, and the treatment process is 480°C for 6 hours. After final rolling C3 with 35% deformation, a 0.38mm strip was obtained, which was subjected to stress relief treatment A3 at 400°C for 60 seconds. After tension bending and straightening, the grain Brass orientation texture, S orientation texture, and The sum of the proportions of R-oriented texture and Copper-oriented texture is 42.5%, of which the proportion of Brass-oriented texture is 6.2%. The obtained copper strip was etched, and the surface roughness after etching was 0.98 μm, and the etching rate reached 16.9 μm/min.

Table 1 Examples and Comparative Examples Alloys and their Composition List

Table 2 Main preparation parameters of the alloys of Examples and Comparative Examples

Table 3 Properties of Examples and Comparative Examples Alloys

The above descriptions are only preferred embodiments of the present invention and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and changes. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principles of the present invention shall be included in the protection scope of the present invention.

Claims (10)

1. A method for improving etching precision of Copper material by utilizing grain orientation is characterized in that for Copper block material with finished product thickness more than or equal to 1.5mm, the method comprises the steps of carrying out short-time high-temperature solid solution S1 on the Copper block material after cold rolling deformation C1 to reduce average grain size of the Copper block material to below 10 mu m, and then carrying out aging treatment A1 to realize that the sum of the Cube orientation texture, S orientation texture, R orientation texture and coppers orientation texture of grains in the Copper block material is less than 30%, so as to form Copper block material mainly with random orientation texture, and the surface roughness after etching is less than 0.5 mu m; for Copper strips with the thickness less than 1.5mm, the method comprises the steps of carrying out cold rolling deformation C1 on the Copper strips, carrying out short-time high-temperature solid solution S2, reducing the average grain size of the Copper strips to below 5 mu m, carrying out cold rolling deformation C2, aging treatment A2, and finally carrying out finish rolling C3 and stress relief treatment A3, so that the sum of the ratio of Brass orientation texture, S orientation texture, R orientation texture and coppers orientation texture in the Copper strips is more than 50%, the ratio of Brass orientation texture is more than 10%, and the surface roughness of the Copper strips after etching is less than 0.4 mu m.

2. The method for improving etching accuracy of copper material by using grain orientation according to claim 1, wherein the deformation amount of the cold rolling deformation C1 is > 85%.

3. The method for improving etching accuracy of copper material by using grain orientation according to claim 2, wherein the deformation amount of the cold rolling deformation C1 is > 95%.

4. The method for improving etching precision of copper material by utilizing grain orientation according to claim 1, wherein the temperature of the short-time high-temperature solid solution S1 is more than 900 ℃, the heat preservation time is less than 10min, and the average grain size is less than 10 μm; the temperature of the short-time high-temperature solid solution S2 is more than 900 ℃, and the heat preservation time is less than 5 minutes, so that the average grain size is less than or equal to 5 mu m.

5. The method for improving etching precision of copper material by utilizing grain orientation according to claim 4, wherein the temperature of the short-time high-temperature solid solution S1 is more than 950 ℃, and the heat preservation time is less than 5min; the temperature of the short-time high-temperature solid solution S2 is more than 950 ℃, and the heat preservation time is less than 2min.

6. The method for improving etching precision of copper material by utilizing grain orientation according to claim 1, wherein the aging treatment A1 and the aging treatment A2 are kept at 300-550 ℃ for 2-10 h, and the size of precipitated phase after aging satisfies d _max ≤0.5μm。

7. The method for improving etching accuracy of copper material by using grain orientation according to claim 1, wherein the deformation amount of the cold rolling deformation C2 is equal to or less than 70%.

8. The method for improving etching accuracy of copper material by using grain orientation according to claim 7, wherein the deformation amount of the cold rolling deformation C2 is 40 to 60%.

9. The method for improving etching accuracy of copper material by using grain orientation according to claim 1, wherein the deformation amount of the finish rolling C3 is equal to or less than 40%.

10. The method for improving etching accuracy of copper material by using grain orientation according to claim 1, wherein the destressing treatment A3 is tension annealing and stretch bending straightening treatment of the copper strip, the process is that the tension annealing is carried out for 30-80 seconds at 300-400 ℃, and the annealed copper strip is subjected to the stretch bending straightening treatment.