An oxygen-free copper strip for ceramic copper-clad plate with grain texture synergistically controlled and a manufacturing method thereof

Abstract

The application provides a kind of grain texture synergic control's ceramic copper-clad plate oxygen-free copper strip, by mass percentage, chemical composition is: Cu is greater than or equal to 99.97%, O is less than or equal to 0.0005%, P: 0.0015%~0.0025%, Mg: 0.005%~0.01%, Sn: 0.005%~0.01%, the remainder is inevitable impurity.The application also provides the preparation method of the above copper strip, based on multiple rolling+intermediate annealing composite process.The application has the advantages that: through the microalloying treatment of oxygen-free copper, simultaneously using multiple rolling+intermediate annealing composite process, by adjusting the reduction distribution, the ratio of deformation texture and recrystallization texture is optimized, effectively inhibits high temperature grain growth;The prepared copper strip has high conductivity, high thermal conductivity, excellent surface quality, low plane anisotropy, and the grain is small and uniform after high temperature annealing, which significantly improves the high temperature resistance.

Description

Technical Field

[0001] This invention relates to the field of copper and copper alloy processing technology, and in particular to an oxygen-free copper strip for ceramic copper-clad laminates with synergistic control of grain texture and its manufacturing method. Background Technology

[0002] With the rapid development of strategic emerging industries such as new energy vehicles, photovoltaics, rail transit, smart grids, and aerospace, the market demand for high-power power electronic devices is experiencing explosive growth. As the core packaging material for these devices, ceramic copper-clad laminates, with their unique advantages of combining the high thermal conductivity, high strength, and excellent insulation properties of ceramic materials with the high conductivity and excellent welding performance of oxygen-free copper, are widely used in key areas such as automotive capacitive pressure sensors, 4G / 5G base stations, and high-voltage frequency converters. Currently, the global market size has reached tens of billions of yuan.

[0003] However, my country's ceramic copper-clad laminate industry faces a serious problem: domestic products are unable to replace imports due to performance shortcomings, causing the entire industry to be constrained by the upstream supply chain. Although domestic companies such as BYD and Fullerwave Semiconductor Technology are actively engaged in research and development, their products still have obvious defects: severe grain coarsening at high temperatures (grain size exceeds 500μm after holding at 1065℃ for 10 minutes, while similar foreign products are only less than 150μm), poor etching performance, low interfacial bonding strength with ceramics, and unstable electrical and thermal conductivity, failing to meet high-end requirements.

[0004] From a technical perspective, ceramic-clad copper (CCL) products impose several stringent performance requirements on oxygen-free copper strips. On one hand, as a power electronics packaging material, it must possess high conductivity (to ensure current carrying capacity), high thermal conductivity (to ensure heat dissipation efficiency), and appropriate tensile strength (to meet mechanical stresses during processing and use). On the other hand, during the high-temperature sintering process with ceramics (900~1000℃), the microstructure must maintain stability. Excessive grain coarsening will cause an "orange peel" texture to form on the copper strip surface, increasing surface roughness and widening the bonding gap with the ceramic, leading to decreased bonding strength or even welding failure. Furthermore, the planar anisotropy of the copper strip must be strictly controlled (IPA ≤ 5%); otherwise, uneven deformation will occur during subsequent stamping, etching, and other processing, affecting product precision.

[0005] Copper, as a typical face-centered cubic (FCC) metal, exhibits grain growth behavior closely related to texture evolution, which is a key reason for performance defects in existing products. Studies have shown that when the cold rolling reduction reaches 80%, strong {001} grains form after annealing. <100> (Cubic) texture, and cubic textured grains with {123} <634> (S), {110} <112> (Brass) and other textured grains exist at 40° <111> Due to special orientation differences, the grain boundary mobility is extremely high, which easily leads to the rapid engulfment of surrounding grains by cubic grains, causing abnormal coarsening at high temperatures. At the same time, traditional improvement methods have limitations: adding alloying elements such as Mg and Ca can pin grain boundaries through second-phase particles, but it will reduce conductivity; simply adjusting the rolling or annealing process is difficult to balance the texture ratio and grain stability, and cannot fundamentally solve the problem.

[0006] Therefore, to overcome the performance bottleneck, it is necessary to achieve a balance between high-temperature stability and overall performance of oxygen-free copper strips through the coordinated control of grain size and texture composition. Summary of the Invention

[0007] The technical problem to be solved by the present invention is to provide an oxygen-free copper strip for ceramic copper-clad laminate with synergistic control of grain texture and its preparation method, so as to avoid the problems of unstable high-temperature grains and difficulty in balancing performance of existing products.

[0008] The present invention solves the above-mentioned technical problems by adopting the following technical solutions:

[0009] An oxygen-free copper strip for ceramic copper-clad laminates with synergistic control of grain texture has the following chemical composition by mass percentage: Cu≥99.97%, O≤0.0005%, P:0.0015%~0.0025%, Mg:0.005%~0.01%, Sn:0.005%~0.01%, with the balance being unavoidable impurities.

[0010] As one of the preferred embodiments of the present invention, the specific chemical composition of the oxygen-free copper strip, by mass percentage, is: Cu: 99.97%, O: 0.0005%, P: 0.0021%, Mg: 0.005%, Sn: 0.01%, with the balance being unavoidable impurities.

[0011] As one of the preferred embodiments of the present invention, the specific chemical composition of the oxygen-free copper strip, by mass percentage, is: Cu: 99.97%, O: 0.0004%, P: 0.0015%, Mg: 0.008%, Sn: 0.007%, with the balance being unavoidable impurities.

[0012] As one of the preferred embodiments of the present invention, the specific chemical composition of the oxygen-free copper strip, by mass percentage, is: Cu: 99.98%, O: 0.0003%, P: 0.0025%, Mg: 0.01%, Sn: 0.005%, with the balance being unavoidable impurities.

[0013] A method for preparing oxygen-free copper strip for ceramic copper-clad laminate with the above-mentioned grain texture synergistic control includes the following steps: (1) melting and casting at 1100~1150℃; (2) heating the ingot at 800~900℃; (3) hot rolling at 700~900℃ with a reduction of 90%~95%; (4) milling the surface after hot rolling; (5) cold rough rolling with a reduction of 80%~83%; (6) intermediate annealing at 500~600℃ for 1~2 min; (7) surface treatment; (8) cold intermediate rolling with a reduction of 80%~83%; (9) annealing at 500~600℃ for 0.5~1 min; (10) surface treatment; (11) cold finish rolling with a reduction of 20%~25%; (12) tension bending and straightening.

[0014] As one of the preferred embodiments of the present invention, the surface treatment is pickling and grinding, using 10%~20% dilute sulfuric acid, grinding speed of 10~30m / min, pressure of 0.1~0.5 MPa, and grinding particles of 1200~2000 mesh.

[0015] As one of the preferred embodiments of the present invention, the bending straightening rate is 80~100m / min, and the elongation after bending straightening is 0.1%~0.3%.

[0016] As one of the preferred embodiments of the present invention, the final product has a thickness of 0.3~1.0mm, a surface roughness Ra=0.2~0.4μm, an average grain size of 10~20μm, and an average grain size of <150μm after being kept at 1065±5℃ for 10min.

[0017] As one of the preferred embodiments of the present invention, the texture component of the final product includes: {001} <100> (cubic) texture 7%~15%, {123} <634> (S) Texture 10%~20%, {112} <111> (Copper type) Texture 11%~18%, {110} <112> (Brass) Texture 4%~10%, {110} <001> (Gaussian) texture 0.3%~2%.

[0018] As one of the preferred embodiments of the present invention, the final product has an conductivity of 99%~100% IACS; a tensile strength of 325~350MPa; and a planar anisotropy parameter (IPA) ≤5%, where IPA=(2Xmax-Xmid-Xmin) / 2Xmax, and X is the tensile strength in the 0°, 45°, and 90° directions.

[0019] The advantages of this invention compared to the prior art are:

[0020] This invention effectively suppresses high-temperature grain growth by microalloying oxygen-free copper and employing a multi-rolling + intermediate annealing composite process. By adjusting the reduction ratio and optimizing the ratio of deformation texture to recrystallization texture, the prepared copper strip exhibits high electrical and thermal conductivity, excellent surface quality (roughness Ra = 0.2~0.4μm), low planar anisotropy (IPA ≤ 5%), and maintains fine and uniform grains after high-temperature annealing (average grain size < 150μm after holding at 1065±5℃ for 10 min), significantly improving high-temperature resistance. Therefore, it successfully solves the problem of high-temperature grain coarsening and performance imbalance in existing products, fully meeting the requirements of high-end ceramic copper-clad laminates. This provides crucial material support for the domestic substitution of high-power power electronic devices in my country, possessing significant economic value and strategic significance.

[0021] The key points are as follows:

[0022] (1) Add trace elements P, Mg and Sn to oxygen-free copper with O content less than 5 ppm. Trace P exists in Cu as Cu3P second phase particles, and trace Mg and Sn exist in Cu as intermetallic compounds or segregate at grain boundaries. During heat treatment or processing, grain boundaries serve as fast channels for atomic diffusion, providing kinetic conditions for the segregation of P, Mg and Sn, resulting in a higher concentration of P, Mg and Sn at grain boundaries than in the matrix. The compounds or segregated layers formed by this grain boundary segregation act like "pinning agents" attached to the grain boundaries. Accordingly, when grains grow, grain boundary migration needs to overcome the resistance brought by the second phase particles. At the same time, element segregation can also reduce the atomic diffusion rate at grain boundaries, slow down the kinetic process of grain growth, thereby effectively hindering dislocation movement and grain boundary migration, suppressing abnormal grain growth, and improving the softening temperature and high temperature resistance of the material.

[0023] (2) The hot rolling reduction rate is 90%~95%, the cold roughing rolling reduction rate is 80%~83%, the cold intermediate rolling reduction rate is 80%~83%, and the cold finishing rolling reduction rate is 20%~25%. Among them, the hot rolling, cold roughing rolling, and intermediate rolling reduction rates are greater than 80%, which makes it easy to form strong {100} after annealing. <001> (Cubic) texture, cold rolling reduction rate is small (20%~25%), in order to increase non-cubic texture components; the final product texture components include cubic, copper mold, S, brass and gauss, and the coexistence of multiple texture components is beneficial to reduce the anisotropy of the strip planarity;

[0024] (3) The surface treatment is pickling and grinding, using 10%~20% dilute sulfuric acid, grinding speed 10~30m / min, pressure 0.1~0.5MPa, grinding particles 1200~2000 mesh, to obtain a clean surface without oxidation, pits, moderate roughness, and surface roughness Ra=0.2~0.4μm, which meets the requirements for composite with ceramic sintering;

[0025] (4) After the finished product is annealed, it is subjected to tension bending straightening at a rate of 80~100m / min. The elongation after tension bending straightening is 0.1%~0.3%. This is to change the orientation of some grains, increase the proportion of S-texture components, reduce the difference in mechanical properties in the longitudinal and transverse directions, and further reduce the anisotropy of the copper strip in the plane (if the elongation after tension bending straightening exceeds 0.3%, the cubic texture and S-texture components will decrease, and the plane anisotropy parameter IPA will increase by 1%). Attached Figure Description

[0026] Figure 1 This is a metallographic diagram of the oxygen-free copper strip finished product after high-temperature annealing in Example 1;

[0027] Figure 2 This is a metallographic diagram of the oxygen-free copper strip finished product after high-temperature annealing in Example 2;

[0028] Figure 3 This is a metallographic diagram of the oxygen-free copper strip finished product after high-temperature annealing in Example 3;

[0029] Figure 4 This is a metallographic diagram of the oxygen-free copper strip finished product after high-temperature annealing in Comparative Example 1;

[0030] Figure 5 This is a metallographic diagram of the oxygen-free copper strip finished product after high-temperature annealing in Comparative Example 2;

[0031] Figure 6 This is a metallographic diagram of the oxygen-free copper strip finished product after high-temperature annealing in Comparative Example 3. Detailed Implementation

[0032] The embodiments of the present invention are described in detail below. These embodiments are implemented based on the technical solution of the present invention, and provide detailed implementation methods and specific operating procedures. However, the scope of protection of the present invention is not limited to the following embodiments. Furthermore, unless otherwise specified, the reagents and materials used in the following embodiments, comparative examples, and experimental examples are all conventional reagents and materials in the art; the methods used, unless otherwise specified, are all conventional methods in the art and will not be described in detail further.

[0033] Example 1

[0034] The oxygen-free copper strip for ceramic copper-clad laminates with grain texture co-control in this embodiment has the following chemical composition by mass percentage: Cu: 99.97%, O: 0.0005%, P: 0.0021%, Mg: 0.005%, Sn: 0.01%, with the balance being unavoidable impurities.

[0035] The preparation method includes the following steps:

[0036] 1. Smelting and casting are carried out in an oxygen-free copper furnace at 1100℃;

[0037] 2. The ingot is heated to 800℃;

[0038] 3. Hot rolling, with an initial rolling temperature of 800℃ and a final rolling temperature of 700℃, and a hot rolling reduction rate of 90%;

[0039] 4. Milling the surface after hot rolling;

[0040] 5. Cold roughing, with a cold roughing reduction rate of 80%;

[0041] 6. The cold-rolled sheet is annealed at 500℃ for 2 minutes.

[0042] 7. Surface treatment: The surface treatment is pickling and grinding, using 10% dilute sulfuric acid, grinding speed 10m / min, pressure 0.4MPa, and grinding particles of 1200 mesh.

[0043] 8. Cold intermediate rolling, with a cold intermediate rolling reduction rate of 80%;

[0044] 9. Anneal the cold-rolled sheet at 500℃ for 1 minute;

[0045] 10. Surface treatment: The surface treatment is pickling and grinding, using 10% dilute sulfuric acid, grinding speed 10m / min, pressure 0.2MPa, and grinding particles of 2000 mesh.

[0046] 11. Cold finishing rolling, with a cold finishing reduction rate of 20%;

[0047] 12. Stretch straightening, stretch straightening rate 80m / min, elongation after stretch straightening 0.1%.

[0048] Example 2

[0049] The oxygen-free copper strip for ceramic copper-clad laminates with grain texture co-control in this embodiment has the following chemical composition by mass percentage: Cu: 99.97%, O: 0.0004%, P: 0.0015%, Mg: 0.008%, Sn: 0.007%, with the balance being unavoidable impurities.

[0050] The preparation method includes the following steps:

[0051] 1. Smelting and casting are carried out in an oxygen-free copper furnace at 1120℃;

[0052] 2. The ingot is heated to 850℃;

[0053] 3. Hot rolling, with an initial rolling temperature of 850℃ and a final rolling temperature of 700℃, and a hot rolling reduction rate of 93%;

[0054] 4. Milling the surface after hot rolling;

[0055] 5. Cold roughing, with a reduction of 82% during cold roughing;

[0056] 6. The cold-rolled sheet is annealed at 550℃ for 1.5 minutes.

[0057] 7. Surface treatment: The surface treatment is pickling and grinding, using 20% ​​dilute sulfuric acid, grinding speed 15m / min, pressure 0.5MPa, and grinding particles of 1300 mesh.

[0058] 8. Cold intermediate rolling, with a cold intermediate rolling reduction rate of 82%;

[0059] 9. The cold-rolled sheet is annealed at 550℃ for 0.8 min;

[0060] 10. Surface treatment: The surface treatment is pickling and grinding, using 20% ​​dilute sulfuric acid, grinding speed 25m / min, pressure 0.5MPa, and grinding particles of 2000 mesh.

[0061] 11. Cold finishing rolling, with a cold finishing reduction rate of 23%;

[0062] 12. Stretch straightening, stretch straightening rate 90m / min, elongation after stretch straightening 0.2%.

[0063] Example 3

[0064] The oxygen-free copper strip for ceramic copper-clad laminates with grain texture co-control in this embodiment has the following chemical composition by mass percentage: Cu: 99.98%, O: 0.0003%, P: 0.0025%, Mg: 0.01%, Sn: 0.005%, with the balance being unavoidable impurities.

[0065] The preparation method includes the following steps:

[0066] 1. Smelting and casting are carried out in an oxygen-free copper furnace at 1150℃;

[0067] 2. The ingot is heated to 900℃;

[0068] 3. Hot rolling, with an initial rolling temperature of 900℃ and a final rolling temperature of 700℃, and a hot rolling reduction rate of 95%;

[0069] 4. Milling the surface after hot rolling;

[0070] 5. Cold roughing, with a cold roughing reduction rate of 83%;

[0071] 6. The cold-rolled sheet is annealed at 600℃ for 1 minute.

[0072] 7. Surface treatment: The surface treatment is pickling and grinding, using 15% dilute sulfuric acid, grinding speed 30m / min, pressure 0.1MPa, and grinding particles of 1200 mesh.

[0073] 8. Cold intermediate rolling, with a cold intermediate rolling reduction rate of 83%;

[0074] 9. Anneal the cold-rolled sheet at 600℃ for 0.5 min;

[0075] 10. Surface treatment: The surface treatment is pickling and grinding, using 15% dilute sulfuric acid, grinding speed 30m / min, pressure 0.1MPa, and grinding particles of 2000 mesh.

[0076] 11. Cold finishing rolling, with a cold finishing reduction rate of 25%;

[0077] 12. Stretch straightening, stretch straightening rate 100m / min, elongation after stretch straightening 0.3%.

[0078] Comparative Example 1

[0079] The oxygen-free copper strip for ceramic copper-clad laminates in this comparative example has the same composition and preparation method as in Example 1. The main difference is that P, Mg, and Sn are not added to the chemical composition of this comparative example.

[0080] Comparative Example 2

[0081] This comparative example provides an oxygen-free copper strip for ceramic copper-clad laminates. Its composition and preparation method are basically the same as those in Example 2. The main difference is that in the preparation method, the cold rolling reduction rate is 60% (82% in Example 2) and the cold finishing rolling reduction rate is 60% (23% in Example 2).

[0082] Comparative Example 3

[0083] The oxygen-free copper strip for ceramic copper-clad laminates in this comparative example has the same composition and preparation method as in Example 3. The main difference is that the surface treatment in the preparation method is only pickling (without grinding), and the bending elongation is 0.4% (0.3% in Example 3).

[0084] Experimental Example 1

[0085] This experimental example is used to verify the comprehensive performance of the oxygen-free copper strip used in the ceramic copper-clad laminate of the present invention.

[0086] The structures of the oxygen-free copper strips for ceramic copper-clad laminates prepared in each embodiment and comparative example of the present invention were observed, and their conductivity, tensile strength and structural stability were tested.

[0087] The results are shown below:

[0088] Example 1: The final product thickness is 1.0 mm, surface roughness Ra = 0.4 μm, and average grain size is 20 μm; the main texture components include: {001} <100> (cubic) texture 7%, {123} <634> (S) Texture 10%, {112} <111> (Copper type) Texture 11%, {110} <112> (Brass) Texture 4%, {110} <001> (Gaussian) texture 0.3%. The copper strip has a conductivity of 100% IACS; tensile strengths in the 0°, 45°, and 90° directions are 340, 334, and 325 MPa, respectively; planar anisotropy parameter (IPA) = 3%; after high-temperature annealing (1070℃ for 10 min), the grain structure is as follows... Figure 1 As shown, the grain size is uniform, with an average grain size of 148 μm.

[0089] Example 2: The final product thickness is 0.5 mm, surface roughness Ra = 0.3 μm, and average grain size is 15 μm; the main texture components include: {001} <100> (cubic) texture 10%, {123} <634> (S) Texture 13%, {112} <111> (Copper type) Texture 16%, {110} <112> (Brass) Texture 6%, {110} <001> (Gaussian) texture 1%. The copper strip has an electrical conductivity of 99.6% IACS; tensile strengths in the 0°, 45°, and 90° directions are 345, 336, and 326 MPa, respectively; planar anisotropy parameter (IPA) = 4%; after high-temperature annealing (1065℃ for 10 min), the grain structure is as follows... Figure 2 As shown, the grain size is uniform, with an average grain size of 130 μm.

[0090] Example 3: The final product thickness is 0.3 mm, surface roughness Ra = 0.2 μm, and average grain size is 10 μm; the main texture components include: {001} <100> (cubic) texture 15%, {123} <634> (S) Texture 20%, {112} <111> (Copper type) Texture 18%, {110} <112> (Brass) Texture 10%, {110} <001> (Gaussian) texture 2%; the copper strip has an conductivity of 99% IACS; tensile strengths in the 0°, 45°, and 90° directions are 350, 337, and 328 MPa, respectively; planar anisotropy parameter (IPA) = 5%; after high-temperature annealing (1060℃ for 10 min), the grain structure is as follows... Figure 3 As shown, the grain size is uniform, with an average grain size of 110 μm.

[0091] Comparative Example 1: The final product thickness is 1.0 mm, surface roughness Ra = 0.4 μm, and average grain size is 24 μm; the main texture components include: {001} <100> (cubic) texture 10%; {123} <634> (S) Texture 9%; {112} <111> (Copper type) Texture 12%; {110} <112> (Brass) Texture 5%; {110} <001> (Gaussian) texture 0.5%. The copper strip has a conductivity of 100% IACS, tensile strengths of 335, 330, and 320 MPa in the 0°, 45°, and 90° directions, respectively, and an interplanar anisotropy parameter (IPA) of 3%. After high-temperature annealing (1070℃ for 10 min), the grain structure is as follows... Figure 4 As shown, the grain size is not uniform, with an average grain size of 400 μm.

[0092] Comparative Example 2: The final product thickness is 0.5 mm, surface roughness Ra = 0.3 μm, and average grain size is 13 μm; the main texture components include: {001} <100> (cubic) texture 5%, {123} <634> (S) Texture 19%, {112} <111> (Copper type) Texture 20%, {110} <112> (Brass) Texture 9%, {110} <001> (Gaussian) texture 1%. The copper strip has a conductivity of 99.6% IACS, tensile strengths of 352, 336, and 326 MPa in the 0°, 45°, and 90° directions, respectively, and an interplanar anisotropy parameter (IPA) of 6%. After high-temperature annealing (1065℃ for 10 min), the grain structure is as follows: Figure 5 As shown, the grain size is relatively uniform, with an average grain size of 200 μm.

[0093] Comparative Example 3: The final product thickness is 0.3 mm, surface roughness Ra = 0.5 μm, and average grain size is 11 μm; the main texture components include: {001} <100> (cubic) texture 14%; {123} <634> (S) Texture 15%; {112} <111> (Copper type) Texture 17%; {110} <112> (Brass) Texture 10%; {110} <001> (Gaussian) texture 2%. The copper strip has an conductivity of 98.5% IACS, tensile strengths of 355, 340, and 328 MPa in the 0°, 45°, and 90° directions, respectively, and an interplanar anisotropy parameter (IPA) of 6%. After high-temperature annealing (1060℃ for 10 min), the grain structure is as follows... Figure 6 As shown, the grain size is relatively uniform, with an average grain size of 120 μm.

[0094] As can be seen from the above results, the oxygen-free copper strips for ceramic copper-clad laminates prepared in the various embodiments of the present invention, in addition to having high electrical and thermal conductivity, also have good surface quality (roughness Ra=0.2~0.4μm), low planar anisotropy (IPA≤5%), fine and uniform grains after high-temperature annealing, and good stability. Compared with the copper strips prepared in Comparative Examples 1~3, the copper strips prepared by the method of the present invention have obvious advantages in comprehensive performance. This indicates that the present invention effectively suppresses high-temperature grain growth by microalloying oxygen-free copper, adjusting the reduction ratio, and optimizing the ratio of deformation texture (S, copper mold, brass, and Gaussian texture) to recrystallization texture (cubic texture). Ideal surface roughness is obtained through surface treatment. The planar anisotropy of the copper strip is reduced by controlling the bending and straightening process.

[0095] Experiment Example 2

[0096] This experimental example is used to verify the bonding strength between the copper strip and the ceramic plate of the present invention.

[0097] Under the same sintering process conditions, the ceramic copper-clad laminate of this invention was bonded to a ceramic plate using oxygen-free copper strip, and corresponding test strips were made (the strip width was uniformly 5 mm and the length was 100 mm). First, 10 mm of the copper strip at one end was peeled off from the ceramic plate as a clamping end. Then, a universal testing machine was used to test the interfacial peel strength (N) of the ceramic copper-clad laminate. The core principle was to measure the peel force between the metal layer and the ceramic substrate using mechanical methods. A commercially available Orustronesium product (ENCW020A) was used as a control.

[0098] The test results are shown in Table 1.

[0099] Table 1. Test results of the bonding strength between oxygen-free copper strip and ceramic plate

[0100]

[0101] The results above show that the bonding strength with ceramic plates is comparable to that of foreign products, and the application effect is good.

[0102] In summary, this invention successfully solves the problems of high-temperature grain coarsening and performance incompatibility in existing products, meets the requirements for high-end ceramic copper-clad laminates, and provides key materials for the domestic substitution of high-power power electronic devices.

[0103] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing oxygen-free copper strip for ceramic copper-clad laminates with synergistic control of grain texture, characterized in that, The oxygen-free copper strip has the following chemical composition by mass percentage: Cu≥99.97%, O≤0.0005%, P:0.0015%~0.0025%, Mg:0.005%~0.01%, Sn:0.005%~0.01%, with the balance being unavoidable impurities; The preparation method includes the following steps: (1) melting and casting at 1100~1150℃; (2) heating the ingot at 800~900℃; (3) hot rolling at 700~900℃ with a reduction rate of 90%~95%; (4) milling the surface after hot rolling; (5) cold rough rolling with a reduction rate of 80%~83%; (6) intermediate annealing at 500~600℃ for 1~2 min; (7) surface treatment; (8) cold intermediate rolling with a reduction rate of 80%~83%; (9) annealing at 500~600℃ for 0.5~1 min; (10) surface treatment; (11) cold finish rolling with a reduction rate of 20%~25%; (12) tension bending and straightening; wherein, the surface treatment is pickling and grinding, using 10%~20% dilute sulfuric acid, grinding speed of 10~30 m / min, and pressure of 0.1~0.

5. MPa, abrasive particles of 1200~2000 mesh; the bending straightening rate is 80~100m / min, and the elongation after bending straightening is 0.1%~0.3%.

2. The method for preparing oxygen-free copper strip for ceramic copper-clad laminate with synergistic grain texture control according to claim 1, characterized in that, The specific chemical composition of the oxygen-free copper strip, by mass percentage, is: Cu: 99.97%, O: 0.0005%, P: 0.0021%, Mg: 0.005%, Sn: 0.01%, with the balance being unavoidable impurities.

3. The method for preparing oxygen-free copper strip for ceramic copper-clad laminate with synergistic grain texture control according to claim 1, characterized in that, The specific chemical composition of the oxygen-free copper strip, by mass percentage, is: Cu: 99.97%, O: 0.0004%, P: 0.0015%, Mg: 0.008%, Sn: 0.007%, with the balance being unavoidable impurities.

4. The method for preparing oxygen-free copper strip for ceramic copper-clad laminate with synergistic grain texture control according to claim 1, characterized in that, The specific chemical composition of the oxygen-free copper strip, by mass percentage, is: Cu: 99.98%, O: 0.0003%, P: 0.0025%, Mg: 0.01%, Sn: 0.005%, with the balance being unavoidable impurities.

5. The method for preparing oxygen-free copper strip for ceramic copper-clad laminate with synergistic grain texture control according to claim 1, characterized in that, The final product has a thickness of 0.3~1.0mm, a surface roughness Ra=0.2~0.4μm, an average grain size of 10~20μm, and an average grain size of <150μm after holding at 1065±5℃ for 10min.

6. The method for preparing oxygen-free copper strip for ceramic copper-clad laminate with synergistic grain texture control according to claim 1, characterized in that, The final texture components include: {001} <100> Texture 7%~15%, {123} <634> Texture 10%~20%, {112} <111> Texture 11%~18%, {110} <112> Texture 4%~10%, {110} <001> Texture 0.3%~2%.

7. The method for preparing oxygen-free copper strip for ceramic copper-clad laminates with synergistic control of grain texture according to claim 1, characterized in that, The final product has an conductivity of 99%~100% IACS, a tensile strength of 325~350MPa, and a planar anisotropy parameter IPA≤5%.

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