A method for preparing titanium anode substrate for electrolytic copper foil

Abstract

This invention provides a method for preparing titanium anode substrates for electrolytic copper foil. The specific steps are: Step 1, preparing titanium anode substrate ingots through two melting processes; Step 2, forging the prepared titanium anode substrate; Step 3, rolling the forged titanium anode substrate. The specific effects of this invention are: the titanium anode substrate prepared by the above method for preparing titanium anode substrates for electrolytic copper foil exhibits significantly improved microstructure and properties, and the enhanced lifespan of titanium anodes produced using this process is significantly increased. This process is relatively simple to operate, requires minimal equipment, and reduces the production cost of titanium anode substrates. It also increases the practical application and operability of this process.

Description

Technical Field

[0001] This invention belongs to the technical field of titanium anode substrate preparation for electrolytic copper foil, and specifically provides a method for preparing titanium anode substrate that improves the microstructure stability and enhances the performance of titanium anodes. Background Technology

[0002] Titanium (Ti), atomic number 22, is a refractory rare light metal. It is a silvery-white metal with low density, high melting point, high specific strength, strong corrosion resistance, good high and low temperature performance, non-magnetic, non-toxic, and biocompatible properties. Its high specific strength is particularly outstanding, comparable to steel, but with half the density. Furthermore, titanium and titanium alloys possess shape memory, superconductivity, and hydrogen storage properties. Currently, titanium and titanium alloys are widely used in chemical engineering, marine engineering, aerospace, military, metallurgy, medical, and sports and leisure fields. Therefore, titanium is an indispensable key material in modern high-tech fields. Titanium anode plates are insoluble anode materials used in the electrochemical industry. They are a new type of high-efficiency electrode material with metallic titanium as the matrix and an active coating mainly composed of noble metal oxides or noble metal materials on the surface. Titanium anodes are now widely used in chemical engineering, electroplating, water treatment, and cathodic protection.

[0003] In the production of electrolytic copper foil, the performance of the titanium anode material is a key factor determining the quality of the copper foil. The microstructure stability of the titanium substrate is fundamental to the superior performance of the titanium anode material. Currently, there are two main problems in the preparation of titanium anode substrates: First, during the casting process, the ingot's microstructure is relatively coarse and uneven, and due to the inherent nature of this microstructure, it cannot be completely eliminated in subsequent processing. Second, during the subsequent preparation of titanium substrate sheets, issues arising from forging, rolling, and heat treatment processes result in surface microcracks and uneven microstructure in the titanium substrate sheets.

[0004] Currently, there are no patented technologies to improve the first type of problem—the hereditary nature of the as-cast microstructure. For the second type of problem, patent application CN115739992A proposes a process for preparing titanium plates for coating, employing a three-stage hot rolling followed by heat treatment annealing. This improves the microstructure stability of the titanium plate to some extent, but the numerous rolling processes are detrimental to cost control. Furthermore, the lack of grinding, pickling, and stress-relief annealing after each rolling step may result in uneven microstructure. Patent application CN 115709221A describes a constrained cold rolling and annealing method for thick titanium plates and the resulting finished titanium plate, employing multiple cold rolling processes. However, due to the limited cold deformation processing capability of pure titanium, and considering that the thickness of titanium anode substrates for electrolytic copper foil is approximately 1 mm, this approach is unsuitable. Patent application CN115961228A describes a method for preparing titanium plates for deep drawing, employing a three-stage hot rolling followed by two-stage cold rolling processes. Due to the different applicable environments, this process is more complex for titanium anode substrates used in electrolytic copper foil production. Furthermore, the lack of atmosphere protection during the entire annealing process of the produced plates significantly affects the microstructure of the plates.

[0005] In summary, to prepare high-performance titanium anode substrates for electrolytic copper foil, improvements are needed in two aspects: first, addressing the coarse and uneven microstructure of titanium ingots, which leads to microstructural inheritance issues; and second, designing a production process for titanium substrates and titanium plates to reduce production costs. Based on these two considerations, the entire production process of titanium anode substrates for electrolytic copper foil must be controlled to obtain high-performance and stable titanium anode substrate plates. Summary of the Invention

[0006] To overcome the shortcomings of existing titanium anode substrates, such as insufficient uniformity of microstructure and unstable performance, this invention proposes a method for preparing titanium anode substrates that improves the microstructure stability and enhances the performance of titanium anodes for electrolytic copper foil. The specific steps of this invention are as follows:

[0007] Step 1: Prepare titanium anode substrate ingots through two melting processes;

[0008] Step 2: Forging the prepared titanium anode as-cast substrate; placing the prepared titanium anode substrate ingot into a box-type high-temperature vacuum heat treatment furnace and heating it to 940-980℃ using a stepped heating method; holding the titanium anode as-cast substrate at 940-980℃ for 2-4 hours; forging the titanium anode substrate ingot using a free forging upsetting method; controlling the thickness of the titanium anode substrate ingot after forging to be 40-50mm;

[0009] Step 3: Roll the forged titanium anode substrate. The rolling process involves two hot rolling cycles and one cold rolling cycle. During hot rolling, the forged titanium anode substrate is placed in a box-type vacuum high-temperature heat treatment furnace and heated to 950–970℃ using a stepped heating method. The as-cast titanium anode substrate at 950–970℃ is held for 1–2 hours. After the first hot rolling, the thickness of the titanium anode substrate is controlled at 25–35 mm, with a deformation per pass ≤10%. After the second hot rolling, the thickness is controlled at 15–25 mm, with a deformation per pass ≤5%. After cold rolling, the thickness is controlled at 10–15 mm, with a deformation per pass ≤5%. After each hot rolling and cold rolling cycle, grinding, pickling, and stress-relieving annealing are performed to obtain titanium anode plates for electrolytic copper foil.

[0010] Further, step 1 includes: the titanium anode substrate ingot is melted using a vacuum consumable arc furnace (VAF), with a primary melting current of 3500–3800 A and a voltage of 28–32 V, and a secondary melting current of 4700–5300 A and a voltage of 29–33 V, at a vacuum degree of 1×10⁻⁶. -1 Pa ~ 1×10 -2 Pa, magnetic stirring is performed during the melting process; the base material composition includes O: 0.07~0.4, B: 0.01~0.3, N: 0.02~0.15, C: 0.02~0.1, with the balance being Ti, and the percentages are atomic percentages; after preparation, the ingot height-to-diameter ratio is 2.1~2.3, the blank cross-section is flat, and the cross-section is perpendicular to the axis.

[0011] Furthermore, step 2 includes: the stepped heating process in the forging process is: between room temperature and 450-500℃, the heating rate is 8-12℃ / min; when the temperature reaches above 500℃, the heating rate is 4-6℃ / min; the forging process requires preheating the tools;

[0012] Furthermore, step 3 includes: the stepped heating process during hot rolling is as follows: the heating rate is 10-14℃ / min between room temperature and 500-550℃; when the temperature reaches above 550℃, the heating rate is 6-8℃ / min; the stress-relief annealing process after hot rolling and cold rolling is as follows: the heating rate is 4-6℃ / min between room temperature and 600-620℃, and the temperature is held for 1-2 hours.

[0013] Furthermore, steps 2 and 3 include: vacuum heat treatment during the forging and rolling process, with a vacuum degree of 1×10⁻⁶. -3 Pa ~ 1×10 -4 Pa.

[0014] The titanium substrate produced by the method for preparing titanium anode substrate for electrolytic copper foil described in this invention can significantly improve the structural stability of the titanium substrate, improve its overall performance, increase its service life, and thus reduce the production cost of the titanium substrate.

[0015] To address the problems existing in current titanium anode substrates for electrolytic copper foil, this invention offers improvements in two aspects. After analysis, the inventors believe that, firstly, to address the issues of coarse, uneven, and hereditary microstructure in the as-cast state, improving the as-cast microstructure of titanium to achieve a fine and uniform structure can solve this problem. Currently, this problem can be solved in two ways: one is microalloying, which involves adding trace amounts of alloying elements to improve the alloy's microstructure; the other is improving the alloy's microstructure through heat treatment and pressure processing, but this method cannot solve the problem of hereditary microstructure. Therefore, the inventors chose microalloying to improve the as-cast microstructure of titanium. Currently, the titanium anode substrate for electrolytic copper foil is TA1 pure titanium sheet. Therefore, during the microalloying process, its microstructure cannot be altered; thus, all microalloying elements are in a solid solution state, and the microstructure is in the α phase. This requires that the content of all microalloying elements cannot exceed their solid solution limit in the α phase. After experimental and theoretical analysis, the inventors ultimately selected oxygen, boron, nitrogen, and carbon as the added microalloying elements. Generally, elements such as oxygen, nitrogen, and carbon are considered impurity elements that are detrimental to the properties of metals. However, current research shows that these elements have a positive impact on the alloy microstructure during the smelting process, and the selected elements are all α-stabilizing elements, which have a stabilizing effect on the α phase of TA1 pure titanium. Through long-term experimental accumulation, the inventors have selected the appropriate range of microalloying element content. After microalloying, a uniform and fine-structured as-cast TA1 pure titanium ingot is obtained.

[0016] To address the second problem with titanium anode substrates for electrolytic copper foil, the inventors systematically reviewed the subsequent forging and rolling processes, ultimately selecting a process of forging + two hot rolling cycles + one cold rolling cycle. Forging temperature is 940–980℃, held for 2–4 hours, resulting in a titanium anode substrate ingot thickness of 40–50 mm after forging. Hot rolling temperature is 950–970℃, held for 1–2 hours, resulting in a titanium anode substrate thickness of 25–35 mm after the first hot rolling cycle, with a deformation per pass ≤10%. After the second hot rolling cycle, the titanium anode substrate thickness is controlled at 15–25 mm, with a deformation per pass ≤5%. After cold rolling, the titanium anode substrate thickness is controlled at 10–15 mm, with a deformation per pass ≤5%. After each hot rolling and cold rolling cycle, grinding, pickling, and stress-relief annealing are performed. The process involves heating from room temperature to 600–620℃ at a rate of 4–6℃ / min, holding for 1–2 hours. Vacuum heat treatment during forging and rolling, with a vacuum degree of 1×10⁻⁶. -3 Pa ~ 1×10 -4Pa. The control of deformation during two hot rolling passes aims to ensure minimal microstructural distortion and maintain structural stability. Each hot rolling and cooling cycle is followed by grinding, pickling, and stress-relief annealing to ensure a uniform and smooth substrate surface, reducing the likelihood of microcracks. Stress-relief annealing also reduces stress within the microstructure, preventing cracking during subsequent rolling processes. All heating processes are conducted in a vacuum furnace to minimize substrate oxidation and eliminate the need for argon protection, thus lowering equipment requirements and costs. Since the alloy's microstructure is influenced by factors such as heat treatment temperature, heating rate, and holding time, extensive experimental data is required. The inventors comprehensively analyzed, screened, and evaluated the experimental parameters to determine reasonable heat treatment process parameters to achieve the objectives of this invention.

[0017] The specific effects achieved by this invention are as follows:

[0018] 1. The titanium anode substrate prepared by the above-mentioned method for preparing titanium anode substrate for electrolytic copper foil has significantly improved microstructure and properties, and the enhanced life of titanium anodes produced by this process is significantly improved.

[0019] 2. This process is relatively simple to operate, requires minimal equipment, and reduces the production cost of titanium anode substrates. This increases the practical application and operability of the process. Attached Figure Description

[0020] Figure 1 The microstructure of the titanium anode substrate used for electrolytic copper foil in Comparative Example 1 is shown in the as-cast state.

[0021] Figure 2 This is the cast microstructure of the titanium anode substrate for electrolytic copper foil in Example 1.

[0022] Figure 3 The microstructure of the titanium anode substrate for electrolytic copper foil in Comparative Example 1 is shown.

[0023] Figure 4 This is the microstructure of the titanium anode substrate plate used for electrolytic copper foil in Example 1.

[0024] Figure 5 This is the lifespan curve of electrolytic copper foil enhanced with titanium anodes in Comparative Example 1.

[0025] Figure 6 This is the lifespan curve of titanium anode enhancement for electrolytic copper foil in Example 1.

[0026] Figure 7 The microstructure of the titanium anode substrate for electrolytic copper foil in Comparative Example and Example 2 is shown in the as-cast state.

[0027] Figure 8 The microstructure of titanium anode substrate for electrolytic copper foil in Comparative Example 2 is shown.

[0028] Figure 9 This is the microstructure of the titanium anode substrate for electrolytic copper foil in Example 2.

[0029] Figure 10 This is the lifespan curve of electrolytic copper foil enhanced with titanium anodes in Comparative Example 2.

[0030] Figure 11 This is the lifespan curve of titanium anode enhancement for electrolytic copper foil in Example 2. Detailed Implementation

[0031] Example 1:

[0032] This embodiment describes a method for preparing a titanium anode substrate for electrolytic copper foil. The specific steps are as follows:

[0033] Step 1: Prepare titanium anode substrate ingots using vacuum consumable arc melting. The primary melting current is 3600A, voltage is 30V, and the secondary melting current is 5000A, voltage is 31V, with a vacuum degree of 1×10⁻⁶. -1 Pa, magnetic stirring is performed during the melting process; the atomic percentage of the base material composition is: 0.2% O, 0.1% B, 0.1% N, 0.05% C, with the balance being Ti. The height-to-diameter ratio of the ingot after preparation is 2.1, the cross-section of the blank is flat, and the cross-section is perpendicular to the axis.

[0034] Step 2: Forging the prepared titanium anode as-cast substrate. The prepared titanium anode substrate ingot is placed in a box-type high-temperature vacuum heat treatment furnace and heated to 950℃ using a stepped heating method; the vacuum degree is 1×10⁻⁶. -3 Pa; The titanium anode as-cast substrate, heated to 950℃, is held at that temperature for 3 hours; the titanium anode substrate ingot is forged using a free forging upsetting method; the thickness of the forged titanium anode substrate ingot is 45mm. The stepped heating process during forging is as follows: the heating rate is 10℃ / min between room temperature and 500℃; when the temperature reaches above 500℃, the heating rate is 5℃ / min; the forging process requires preheating the tools.

[0035] Step 3: Roll the forged titanium anode substrate. The rolling process involves two hot rolling cycles and one cold rolling cycle. During hot rolling, the forged titanium anode substrate is placed in a box-type vacuum high-temperature heat treatment furnace and heated to 960℃ using a stepped heating method; the vacuum degree is 1×10⁻⁶. -3Pa; The stepped heating process in the hot rolling process is as follows: from room temperature to 530℃, the heating rate is 12℃ / min; when the temperature reaches above 530℃, the heating rate is 6℃ / min; the titanium anode cast substrate heated to 960℃ is held for 1.5h; after the first hot rolling, the thickness of the titanium anode substrate is controlled at 30mm, and the deformation per pass is 8%; after the second hot rolling, the thickness of the titanium anode substrate is controlled at 15mm, and the deformation per pass is 4%; after cold rolling, the thickness of the titanium anode substrate is controlled at 10mm, and the deformation per pass is 3%; after each hot rolling and cold rolling, grinding, pickling, and stress-relief annealing are performed. The stress-relief annealing process after hot rolling and cold rolling is as follows: the temperature is raised from room temperature to 600℃, the heating rate is 5℃ / min, and the holding time is 2h; finally, titanium anode plates for electrolytic copper foil are obtained.

[0036] Comparative Example 1:

[0037] Step 1: Prepare titanium anode substrate ingots using vacuum consumable arc melting. The primary melting current is 3600A, voltage is 30V, and the secondary melting current is 5000A, voltage is 31V, with a vacuum degree of 1×10⁻⁶. -1 Pa, magnetic stirring is carried out during the melting process; the base material is grade 0 sponge titanium, and the height-to-diameter ratio of the ingot after preparation is 2.1. The blank cross-section is flat and perpendicular to the axis.

[0038] Step 2: Forging the prepared titanium anode as-cast substrate. The prepared titanium anode substrate ingot is placed in a box-type high-temperature vacuum heat treatment furnace and heated to 950℃ using a stepped heating method; the vacuum degree is 1×10⁻⁶. -3 Pa; The titanium anode as-cast substrate, heated to 950℃, is held at that temperature for 3 hours; the titanium anode substrate ingot is forged using a free forging upsetting method; the thickness of the forged titanium anode substrate ingot is 45mm. The stepped heating process during forging is as follows: the heating rate is 10℃ / min between room temperature and 500℃; when the temperature reaches above 500℃, the heating rate is 5℃ / min; the forging process requires preheating the tools.

[0039] Step 3: Roll the forged titanium anode substrate. The rolling process involves two hot rolling cycles and one cold rolling cycle. During hot rolling, the forged titanium anode substrate is placed in a box-type vacuum high-temperature heat treatment furnace and heated to 960℃ using a stepped heating method; the vacuum degree is 1×10⁻⁶. -3Pa; The stepped heating process in the hot rolling process is as follows: from room temperature to 530℃, the heating rate is 12℃ / min; when the temperature reaches above 530℃, the heating rate is 6℃ / min; the titanium anode cast substrate heated to 960℃ is held for 1.5h; after the first hot rolling, the thickness of the titanium anode substrate is controlled at 30mm, and the deformation per pass is 8%; after the second hot rolling, the thickness of the titanium anode substrate is controlled at 15mm, and the deformation per pass is 4%; after cold rolling, the thickness of the titanium anode substrate is controlled at 10mm, and the deformation per pass is 3%; after each hot rolling and cold rolling, grinding, pickling, and stress-relief annealing are performed. The stress-relief annealing process after hot rolling and cold rolling is as follows: the temperature is raised from room temperature to 600℃, the heating rate is 5℃ / min, and the holding time is 2h; finally, titanium anode plates for electrolytic copper foil are obtained.

[0040] The experimental results of Example 1 and Comparative Example 1 showed significant differences. Figure 1 This is the as-cast microstructure of the titanium anode substrate used for electrolytic copper foil in Comparative Example 1. It can be seen that the as-cast microstructure after smelting is relatively coarse and has poor uniformity. Figure 2 This is the as-cast microstructure of the titanium anode substrate for electrolytic copper foil in Example 1. After microalloying, its as-cast microstructure exhibits a uniform and fine structure, significantly improving the microstructure of the alloy and solving the problem of the inheritance of as-cast microstructure in subsequent processes. Figure 3 The microstructure of the titanium anode substrate for electrolytic copper foil in Comparative Example 1 is shown. Although the subsequent substrate preparation process was adjusted, the microstructure of the substrate is not uniform due to the inheritance of the as-cast microstructure, resulting in poor consistency. Figure 4 This is the microstructure of the titanium anode substrate for electrolytic copper foil in Example 1. It can be seen that the microstructure of the substrate exhibits fine, uniform equiaxed grains, with good consistency in the structure.

[0041] Both Example 1 and Comparative Example 1 were subjected to the same subsequent sandblasting, pickling, and anodic coating processes to obtain titanium anode plates for electrolytic copper foil. The enhanced lifespan of both plates was then tested. Figure 5 This is the lifespan curve of electrolytic copper foil enhanced with titanium anodes in Comparative Example 1. Figure 6 This is the enhanced life curve of the titanium anode used for electrolytic copper foil in Example 1. The enhanced life of Example 1 is 25 days, and that of Comparative Example 1 is 17 days. The experimental results show that the process of Example 1 can significantly improve the microstructure stability of the titanium anode substrate used for electrolytic copper foil, enhance the performance of the titanium anode, and thus reduce production costs.

[0042] Example 2:

[0043] This embodiment describes a method for preparing a titanium anode substrate for electrolytic copper foil. The specific steps are as follows:

[0044] Step 1: Prepare titanium anode substrate ingots using vacuum consumable arc melting. The primary melting current is 3700A, voltage is 28V, and the secondary melting current is 4900A, voltage is 30V, with a vacuum degree of 1×10⁻⁶. -2 Pa, magnetic stirring is performed during the melting process; the atomic percentage of the base material composition is: 0.1% O, 0.15% B, 0.08% N, 0.1% C, with the balance being Ti. The height-to-diameter ratio of the prepared ingot is 2.2, the blank cross-section is flat, and the cross-section is perpendicular to the axis.

[0045] Step 2: Forging the prepared titanium anode as-cast substrate. The prepared titanium anode substrate ingot is placed in a box-type high-temperature vacuum heat treatment furnace and heated to 970℃ using a stepped heating method; the vacuum degree is 1×10⁻⁶. -4 Pa; The titanium anode as-cast substrate, heated to 970℃, is held for 2 hours; the titanium anode substrate ingot is forged using a free forging upsetting method; the thickness of the forged titanium anode substrate ingot is 40mm. The stepped heating process during forging is as follows: the heating rate is 8℃ / min between room temperature and 460℃; when the temperature reaches above 460℃, the heating rate is 6℃ / min; the forging process requires preheating of the tools.

[0046] Step 3: Roll the forged titanium anode substrate. The rolling process involves two hot rolling cycles and one cold rolling cycle. During hot rolling, the forged titanium anode substrate is placed in a box-type vacuum high-temperature heat treatment furnace and heated to 970℃ using a stepped heating method; the vacuum degree is 1×10⁻⁶. -3 Pa; The stepped heating process in the hot rolling process is as follows: from room temperature to 530℃, the heating rate is 12℃ / min; when the temperature reaches above 530℃, the heating rate is 6℃ / min; the titanium anode cast substrate heated to 970℃ is held for 1 hour; after the first hot rolling, the thickness of the titanium anode substrate is controlled at 25mm, and the deformation per pass is 7%; after the second hot rolling, the thickness of the titanium anode substrate is controlled at 16mm, and the deformation per pass is 3%; after cold rolling, the thickness of the titanium anode substrate is controlled at 11mm, and the deformation per pass is 2%; after each hot rolling and cold rolling, grinding, pickling, and stress-relief annealing are performed. The stress-relief annealing process after hot rolling and cold rolling is as follows: the temperature is raised from room temperature to 620℃, the heating rate is 6℃ / min, and the holding time is 1 hour; finally, titanium anode plates for electrolytic copper foil are obtained.

[0047] Comparative Example 2:

[0048] This embodiment describes a method for preparing a titanium anode substrate for electrolytic copper foil. The specific steps are as follows:

[0049] Step 1: Prepare titanium anode substrate ingots using vacuum consumable arc melting. The primary melting current is 3700A, voltage is 28V, and the secondary melting current is 4900A, voltage is 30V, with a vacuum degree of 1×10⁻⁶. -2Pa, magnetic stirring is performed during the melting process; the atomic percentage of the base material composition is: 0.1% O, 0.15% B, 0.08% N, 0.1% C, with the balance being Ti. The height-to-diameter ratio of the prepared ingot is 2.2, the blank cross-section is flat, and the cross-section is perpendicular to the axis.

[0050] Step 2: Forging the prepared titanium anode as-cast substrate. The prepared titanium anode substrate ingot is placed in a box-type high-temperature heat treatment furnace and heated to 970℃; the titanium anode as-cast substrate heated to 970℃ is held at this temperature for 2 hours; the titanium anode substrate ingot is forged using a free forging upsetting method.

[0051] Step 3: Rolling the forged titanium anode substrate. Rolling is performed using two hot rolling cycles and one cold rolling cycle. During hot rolling, the forged titanium anode substrate is placed in a box-type high-temperature heat treatment furnace and heated to 970℃, held for 1 hour. After the first hot rolling, the thickness of the titanium anode substrate is controlled at 25mm; after the second hot rolling, the thickness is controlled at 16mm; after cold rolling, the thickness is controlled at 11mm. After each hot rolling and cold rolling cycle, grinding, pickling, and stress-relief annealing are performed. The stress-relief annealing process after hot and cold rolling involves raising the temperature from room temperature to 620℃ and holding for 1 hour. Finally, titanium anode plates for electrolytic copper foil are obtained.

[0052] Because Example 2 and Comparative Example 2 used the same process parameters in their smelting processes, the as-cast microstructure of their titanium anode substrates was identical, such as... Figure 7 As shown. However, the subsequent forging and rolling processes of Example 2 and Comparative Example 2 differ. In the comparative example, the forging and rolling process did not employ a stepped heating method, and the heating and holding processes were not carried out in a vacuum furnace. Therefore, the process of Comparative Example 2 is simpler, requires less equipment, and is less expensive. However... Figure 8 The microstructure of the titanium anode substrate used for electrolytic copper foil in Comparative Example 2 is shown. Figure 9 This is the microstructure of the titanium anode substrate for electrolytic copper foil in Example 2. It can be seen that although the microstructure uniformity of both Example 2 and Comparative Example 2 is good, there are significant differences in grain size. Due to the simpler process in Comparative Example 2, the microstructure is coarser, and randomly distributed needle-like structures exist within the grains.

[0053] Example 2 and Comparative Example 2 were subjected to the same subsequent sandblasting, pickling, and anodic coating processes to obtain titanium anode plates for electrolytic copper foil. The enhanced lifespan of both plates was then tested. Figure 10 This is the lifespan curve of electrolytic copper foil enhanced with titanium anodes in Comparative Example 2. Figure 11This is the enhanced life curve of the titanium anode used for electrolytic copper foil in Example 2. The enhanced life of Example 2 is 25 days, while that of Comparative Example 2 is 16 days. The above experimental results indicate that subsequent thermal processing requires more detailed and rigorous process parameters. The process of Example 2 can significantly improve the microstructure stability of the titanium anode substrate used for electrolytic copper foil, enhance the performance of the titanium anode, and thus reduce production costs.

Claims

1. A method for preparing a titanium anode substrate for electrolytic copper foil, characterized in that, The specific steps are as follows: Step 1: Prepare titanium anode substrate ingots through two melting processes. The titanium anode substrate ingots are melted using a vacuum consumable arc melting process. The first melting process uses a current of 3500–3800 A and a voltage of 28–32 V, while the second melting process uses a current of 4700–5300 A and a voltage of 29–33 V, with a vacuum degree of 1×10⁻⁶. -1 Pa ~ 1×10 -2 Pa, magnetic stirring is performed during the melting process; the base material composition includes O: 0.07~0.4, B: 0.01~0.3, N: 0.02~0.15, C: 0.02~0.1, with the balance being Ti, and the percentages are atomic percentages; Step 2: Forging the prepared titanium anode cast substrate; placing the prepared titanium anode substrate ingot into a box-type high-temperature vacuum heat treatment furnace and heating it to 940-980℃ using a stepped heating method, with a vacuum degree of 1×10⁻⁶. -3 Pa ~ 1×10 - 4 Pa; The titanium anode as-cast substrate heated to 940-980℃ is held for 2-4 hours; the titanium anode substrate ingot is forged using a free forging upsetting method; the thickness of the titanium anode substrate ingot after forging is controlled at 40-50mm; the stepped heating process is as follows: between room temperature and 450-500℃, the heating rate is 8-12℃ / min; when the temperature reaches above 500℃, the heating rate is 4-6℃ / min; Step 3: Roll the forged titanium anode substrate; the rolling process involves two hot rolling cycles and one cold rolling cycle. During hot rolling, the forged titanium anode substrate is placed in a box-type vacuum high-temperature heat treatment furnace and heated to 950–970°C using a stepped heating method, with a vacuum degree of 1×10⁻⁶. -3 Pa ~ 1×10 -4 Pa; The stepped heating process is as follows: between room temperature and 500-550℃, the heating rate is 10-14℃ / min; when the temperature reaches above 550℃, the heating rate is 6-8℃ / min; the titanium anode cast substrate heated to 950-970℃ is held for 1-2 hours; after the first hot rolling, the thickness of the titanium anode substrate is controlled at 25-35mm, and the deformation per pass is ≤10%; after the second hot rolling, the thickness of the titanium anode substrate is controlled at 15-25mm, and the deformation per pass is ≤5%; after the cold rolling, the thickness of the titanium anode substrate is controlled at 10-15mm, and the deformation per pass is ≤5%; after each hot rolling and cold rolling, grinding, pickling, and stress-relief annealing are performed. The stress-relief annealing process is as follows: between room temperature and 600-620℃, the heating rate is 4-6℃ / min, and the holding time is 1-2 hours to obtain titanium anode plates for electrolytic copper foil.

2. The method for preparing titanium anode substrate for electrolytic copper foil as described in claim 1, characterized in that, After preparation, the height-to-diameter ratio of the ingot is 2.1 to 2.3, the cross-section of the billet is flat, and the cross-section is perpendicular to the axis.

3. The method for preparing titanium anode substrate for electrolytic copper foil as described in claim 1, characterized in that, The forging process requires preheating the tools.

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