Large-size titanium-based cathode roller and processing technology thereof

Abstract

The present application relates to the technical field of titanium-based cathode roller, in particular to a large-size titanium-based cathode roller and a processing technology thereof, comprising the following processes: step one, taking a blank to carry out high-temperature blooming upsetting, punching, hole expanding, mandrel drawing, and obtaining a ring blank; step two, taking the ring blank obtained in step one to perform dressing and marking inspection; step three, taking the ring blank obtained in step two to perform turning, and obtaining a ring piece; step four, taking the ring piece obtained in step three to perform post-processing, and obtaining a cathode roller. The present application uses a new technology of forging-rolling combination to successfully produce a whole seamless ring piece at one time, which can effectively meet the requirements of the cathode roller on the morphology and mechanical properties at the microstructure level, and eliminate the occurrence of periodic bright band during the production of copper foil by the customer.

Description

Technical Field

[0001] This invention relates to the field of titanium-based cathode roller technology, specifically to a large-size titanium-based cathode roller and its processing technology. Background Technology

[0002] Copper foil, as one of the fundamental materials in the electronics industry, is often referred to as the "neural network" for signal and power transmission in electronic products. Electrolysis is a mainstream and efficient production method for copper foil, and the cathode roller, as a key piece of equipment and component in the production of electrolytic copper foil, is the heart of the complete electrolysis system. The traditional manufacturing method for the cathode roller typically involves first rolling a titanium plate into a cylinder, then welding the seam; heating the weld and heat-affected zone at a temperature controlled within the range of 750–950℃, while cooling and protecting the undeformed substrate; and then upsetting and forging the weld seam; repeating this process multiple times to deform the weld seam repeatedly, with each deformation exceeding 30%. Traditional copper foil processing methods have certain drawbacks, namely the presence of weld seams and differences in weld microstructure between the weld seam and the substrate microstructure, resulting in periodic bright bands on the foil during later copper foil production. Therefore, we propose a large-size titanium-based cathode roller and its processing technology. Summary of the Invention

[0003] The purpose of this invention is to provide a large-size titanium-based cathode roller and its processing technology to solve the problems mentioned in the background art.

[0004] To solve the above-mentioned technical problems, the present invention provides the following technical solution: a processing technology for a large-size titanium-based cathode roller, comprising the following processes:

[0005] Step 1: Take the billet and perform high-temperature upsetting and drawing, punching, hole enlargement, and mandrel drawing to obtain a ring billet;

[0006] Step 2: Take the ring blank obtained in Step 1, grind it to remove damage, scribing and inspect it;

[0007] Step 3: Take the ring blank obtained in Step 2 and turn it to obtain the ring part;

[0008] Step 4: Take the ring obtained in Step 3 and perform post-processing to obtain the cathode roller.

[0009] Furthermore, the billet in step one is titanium and titanium alloy with a height-to-diameter ratio ≤ 2:1; this helps to avoid the formation of double-bulge-shaped blanks during the upsetting process.

[0010] In step one, the billet undergoes three high-temperature upsetting and drawing processes at 700–800℃. A 6500T press is used for upsetting until the ring billet height is 1.1 times the ring height, controlling the ring billet height to meet the height requirements of the cathode roller. Then, punching and reaming are performed, ensuring the ratio of the ring billet diameter to the punch diameter is ≥4:1 to prevent material inward turning during punching. The ring billet is then reamed using a frame, with the inner diameter within 1.25 times the diameter of the vertical ring rolling mill mandrel to prevent excessive gap between the billet and mandrel during ring rolling, which would hinder height growth and affect the end rolling effect. Finally, the mandrel is drawn to 1.1 times the ring height.

[0011] As the diameter of the cathode roller gradually increases, a series of plastic processing processes are required. To meet its forming performance requirements, the cathode roller manufactured in this invention uses industrial pure titanium TA1 as the blank, which includes the following mass composition: iron: 0.19%~0.23%, carbon: 0.01%~0.02%, oxygen: 0.09%~0.10%, nitrogen: 0.01%~0.02%, hydrogen: 0.001%, other impurities <0.2%, and the balance being titanium.

[0012] Furthermore, after obtaining the ring billet, end rolling is performed to the required dimensions; specifically, the following processes are included:

[0013] Asynchronous rolling is used to roll the ring billet 6 to 9 times, with a processing rate of 26% to 36%; then synchronous rolling is used to roll the ring billet 2 to 3 times, with a processing rate of 22% to 25%, and the speed ratio of the upper roll to the lower roll is 3:2.

[0014] The wall thickness of the end-rolled ring billet is 40–52 mm.

[0015] Furthermore, in step two, the ring blank undergoes 100% grinding and damage removal to prevent downtime due to defects during ring rolling and to avoid unnecessary heating difficulties caused by incomplete one-time forming. The blank dimensions are estimated with a reduction of 1.1% to 1.5% to prevent insufficient machining allowance after blank reduction. The ovality of the ring blank is controlled within 10mm. Marking on the platform is to check for any missing material in the ring blank and to prevent subsequent machining errors.

[0016] Furthermore, in step three, a vertical lathe is used to perform low-speed coolant turning of the finished ring part to prevent oxidation of the ring part surface caused by machining.

[0017] In the above technical solution, the new technology of combining forging and rolling is used to successfully produce a seamless ring in one go, which can effectively meet the requirements of cathode roller in terms of morphology and mechanical properties at the microstructure level, and eliminate the occurrence of periodic bright bands when customers produce copper foil later.

[0018] By combining asynchronous and synchronous rolling, the ring billet undergoes significant deformation, resulting in intense plastic deformation, refined grain structure, and a marked reduction in grain size, forming nanocrystals. Slip and lattice rotation are the primary deformation modes, increasing dislocation density and causing in-situ dynamic recrystallization of the ring billet structure, forming a deformed structure. This grain refinement, in turn, improves the strength and hardness of the manufactured ring.

[0019] Furthermore, the post-processing in step four includes heat treatment and passivation processes.

[0020] Furthermore, the heat treatment process is as follows: annealing at 200–400°C for 20–30 minutes.

[0021] However, the rolling process results in a large amount of residual stress and lattice distortion within the ring billet's microstructure, necessitating heat treatment. Lower heat treatment temperatures can prevent recrystallization of the ring's grain structure, which would otherwise lead to larger grain sizes. After heat treatment, lattice distortion and residual stress in the ring billet are reduced, grain size does not increase significantly, the nanocrystalline structure is preserved, and dislocations at / near grain boundaries tend to become more ordered. This is more conducive to improving the grain size, microstructure, and grain size of the cathode roll surface after passivation.

[0022] Furthermore, the passivation process is as follows:

[0023] The heat-treated ring was placed in a passivation solution and hydrothermally reacted at 210–230°C for 12–24 hours; then removed, cooled to room temperature, washed, and dried.

[0024] Furthermore, the passivation solution contains the following components by mass: 2.2–2.5 g / L ammonium titanate, 3.4–3.6 g / L hexamethylenetetramine, and 0.070–0.075 g / L diethanolamine.

[0025] Furthermore, the ammonium titanate is prepared by the following process:

[0026] Titanium dioxide was placed in potassium hydroxide solution and hydrothermally reacted at 210–230 °C for 24 h. After cooling to room temperature, the precipitate was taken, washed with water, and placed in ammonium nitrate solution and stirred for 4–8 h. After centrifugation, the reaction was repeated several times, washed with water, and dried under vacuum at 60 °C.

[0027] Titanium dioxide: P25 nano titanium dioxide, sourced from Evonik Specialty Chemicals (Shanghai) Co., Ltd.;

[0028] The concentration of potassium hydroxide solution is 10 mol / L, and the concentration of ammonium nitrate solution is 0.1 mol / L;

[0029] The ratio of titanium dioxide to potassium hydroxide solution is 3.5–4.0 g: 100 mL.

[0030] Furthermore, before passivation, the surface was polished step by step with 150#-1200# sandpaper, ultrasonically cleaned in anhydrous ethanol for 30 minutes, rinsed with deionized water, and dried.

[0031] In the above technical solution, as the temperature increases, ammonium titanate undergoes hydrolysis, producing titanium hydroxide, ammonium ions, and potassium ions. A dehydration reaction occurs between Ti-OH groups in the titanium hydroxide, forming crystal nuclei that grow and gradually form titanium dioxide crystals, which are then deposited on the surface of the ring to form rod-shaped titanium dioxide nanostructures. Influenced by the amino and hydroxyl groups in diethanolamine, the (001) crystal plane in the titanium dioxide crystal selectively adsorbs diethanolamine, inhibiting the growth of this crystal plane. The (101), (010), and other crystal planes undergo orientation and adhesion, resulting in the deposition of spherical titanium dioxide nanoparticles on the surface of the ring. This improves the surface grain size of the cathode roller, enhances its corrosion resistance, and prevents surface corrosion caused by liquid temperature, acidity, and copper ion concentration during the electrolytic manufacturing of copper foil. This corrosion leads to uneven passivation of the cathode roller surface, resulting in differences in the smoothness of the copper foil surface and affecting the microstructure and roughness of the copper foil substrate.

[0032] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0033] 1. The large-size titanium-based cathode roller and its processing technology of the present invention successfully produce a seamless ring in one step by adopting a new technology combining forging and rolling. This effectively meets the requirements of the cathode roller in terms of morphology and mechanical properties at the microstructure level, and eliminates the occurrence of periodic bright bands when customers produce copper foil later.

[0034] 2. The large-size titanium-based cathode roll and its processing technology of the present invention, through the combination of asynchronous rolling and synchronous rolling, cause significant deformation of the ring billet, resulting in strong plastic deformation, refined grain structure, and a significant reduction in grain size, forming nanocrystals. Slip and lattice rotation are the main deformation modes, increasing dislocation density and causing in-situ dynamic recrystallization of the ring billet structure, forming a deformed structure. While refining the grains, this process also improves the strength and hardness of the manufactured ring.

[0035] 3. The large-size titanium-based cathode roller and its processing technology of the present invention avoid recrystallization of the ring blank grain structure at a lower heat treatment temperature, which would lead to an increase in grain size. After heat treatment, the lattice distortion and residual stress in the ring blank are reduced, the grain size does not increase significantly, the nanocrystalline structure in the structure is preserved, and the dislocations at / near the grain boundaries of the surface defect structure tend to be ordered, which is more conducive to the improvement of the surface grain size, microstructure, and grain size of the cathode roller after the passivation process.

[0036] 4. The large-size titanium-based cathode roller and its processing technology of the present invention, through the setting of the passivation process, deposits titanium dioxide spherical nanoparticles on the surface of the ring, thereby improving the surface grain size of the cathode roller, enhancing its corrosion resistance, and avoiding the surface corrosion of the cathode roller caused by liquid temperature, acidity, copper ion concentration, etc. during the electrolytic manufacturing of copper foil, which would lead to uneven performance of the passivation layer on the surface of the cathode roller, resulting in roughness differences in the smooth surface of the copper foil, and affecting the microstructure and roughness of the copper foil substrate. Detailed Implementation

[0037] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0038] In the following embodiments, the diameter of the cathode roller is Φ2700mm;

[0039] Titanium dioxide: P25 nano-grade titanium dioxide, sourced from Evonik Specialty Chemicals (Shanghai) Co., Ltd.

[0040] Example 1: A processing technology for a large-size titanium-based cathode roller, comprising the following processes:

[0041] The billet is selected from industrial pure titanium TA1 with a height-to-diameter ratio of 2:1, and includes the following mass composition: iron: 0.21%, carbon: 0.013%, oxygen: 0.097%, nitrogen: 0.012%, hydrogen: 0.001%, other impurities <0.2%, and the balance is titanium;

[0042] Step 1: Take the billet and use a 6500T press to upset the billet until the height of the ring billet is 1.1 times the height of the ring piece; Punching: The diameter of the ring billet is 4 times the diameter of the punch. The ring billet is enlarged using a frame, and the inner diameter is 1.25 times the diameter of the mandrel of the vertical ring rolling mill; The mandrel is then lengthened; End rolling: Asynchronous rolling is used to roll the ring billet 6 times, with a processing rate of 26%; Then synchronous rolling is used to roll the ring billet 2 times, with a processing rate of 22%. The speed ratio of the upper and lower rolls is 3:2 to obtain the ring billet with a wall thickness of 52mm; The height of the ring billet is 1.1 times the height of the ring piece;

[0043] Step 2: Take the ring blank obtained in Step 1, grind it to remove damage, scribing and inspect it;

[0044] Step 3: Take the ring blank obtained in Step 2 and turn it to obtain the ring part;

[0045] Step 4: The ring obtained in Step 3 is subjected to heat treatment. The heat treatment process is: annealing at 200℃ for 20 min. Passivation treatment is performed as follows: 35g of titanium dioxide is placed in 1L of potassium hydroxide solution (10mol / L) and hydrothermally reacted at 210℃ for 24h; after cooling to room temperature, the precipitate is taken, washed with water until the pH of the system is 9, and placed in 1L of ammonium nitrate solution (0.1mol / L) and stirred for 4h. After centrifugation, the reaction is repeated several times, washed with water, and vacuum dried at 60℃ to obtain ammonium titanate; the ring obtained after heat treatment is placed in the passivation solution and hydrothermally reacted at 210℃ for 12h; after removal, it is cooled to room temperature, washed, and dried to obtain the cathode roller; the passivation solution contains the following mass components: 2.2g / L ammonium titanate, 3.4g / L hexamethylenetetramine, and 0.070g / L diethanolamine.

[0046] Example 2: A processing technology for a large-size titanium-based cathode roller, comprising the following processes:

[0047] The billet is selected from industrial pure titanium TA1 with a height-to-diameter ratio of 1.8:1, and includes the following mass composition: iron: 0.21%, carbon: 0.013%, oxygen: 0.097%, nitrogen: 0.012%, hydrogen: 0.001%, other impurities <0.2%, and the balance is titanium;

[0048] Step 1: Take the billet and use a 6500T press to upset the billet until the height of the ring billet is 1.1 times the height of the ring piece; Punching: The diameter of the ring billet is 4 times the diameter of the punch. The ring billet is enlarged using a frame, and the inner diameter is 1.25 times the diameter of the mandrel of the vertical ring rolling mill; The mandrel is then lengthened; End rolling: Asynchronous rolling is used to roll the ring billet 8 times, with a processing rate of 32%; Then synchronous rolling is used to roll the ring billet 2 times, with a processing rate of 22%. The speed ratio of the upper and lower rolls is 3:2 to obtain the ring billet with a wall thickness of 45mm; The height of the ring billet is 1.1 times the height of the ring piece;

[0049] Step 2: Take the ring blank obtained in Step 1, grind it to remove damage, scribing and inspect it;

[0050] Step 3: Take the ring blank obtained in Step 2 and turn it to obtain the ring part;

[0051] Step 4: The ring obtained in Step 3 is subjected to heat treatment. The heat treatment process is: annealing at 300℃ for 25 minutes. Passivation treatment is performed as follows: 38g of titanium dioxide is placed in 1L of potassium hydroxide solution (10mol / L) and hydrothermally reacted at 220℃ for 24 hours; after cooling to room temperature, the precipitate is taken, washed with water until the pH of the system is 8, and placed in 1L of ammonium nitrate solution (0.1mol / L) and stirred for 6 hours. After centrifugation and repeated several times, it is washed with water and vacuum dried at 60℃ to obtain ammonium titanate; the ring obtained after heat treatment is placed in the passivation solution and hydrothermally reacted at 220℃ for 18 hours; after removal, it is cooled to room temperature, washed, and dried to obtain the cathode roller; the passivation solution contains the following mass components: 2.4g / L ammonium titanate, 3.5g / L hexamethylenetetramine, and 0.072g / L diethanolamine.

[0052] Example 3: A processing technology for a large-size titanium-based cathode roller, comprising the following processes:

[0053] The billet is selected from industrial pure titanium TA1 with a height-to-diameter ratio of 1.5:1, and includes the following mass composition: iron: 0.21%, carbon: 0.013%, oxygen: 0.097%, nitrogen: 0.012%, hydrogen: 0.001%, other impurities <0.2%, and the balance is titanium;

[0054] Step 1: Take the billet and use a 6500T press to upset the billet until the height of the ring billet is 1.1 times the height of the ring piece; Punching: The diameter of the ring billet is 4 times the diameter of the punch. The ring billet is enlarged using a frame, and the inner diameter is 1.25 times the diameter of the mandrel of the vertical ring rolling mill; The mandrel is then lengthened; End rolling: Asynchronous rolling is used to roll the ring billet 9 times, with a processing rate of 36%; Then synchronous rolling is used to roll the ring billet 3 times, with a processing rate of 25%. The speed ratio of the upper and lower rolls is 3:2 to obtain the ring billet with a wall thickness of 40mm; The height of the ring billet is 1.1 times the height of the ring piece;

[0055] Step 2: Take the ring blank obtained in Step 1, grind it to remove damage, scribing and inspect it;

[0056] Step 3: Take the ring blank obtained in Step 2 and turn it to obtain the ring part;

[0057] Step 4: The ring obtained in Step 3 is subjected to heat treatment. The heat treatment process is: annealing at 400℃ for 30 min. Passivation treatment is performed as follows: 40g of titanium dioxide is placed in 1L of potassium hydroxide solution (10mol / L) and hydrothermally reacted at 230℃ for 24h; after cooling to room temperature, the precipitate is taken, washed with water until the pH of the system is 7, and placed in 1L of ammonium nitrate solution (0.1mol / L) and stirred for 8h. After centrifugation, the reaction is repeated several times, washed with water, and vacuum dried at 60℃ to obtain ammonium titanate; the ring obtained after heat treatment is placed in the passivation solution and hydrothermally reacted at 230℃ for 24h; after removal, it is cooled to room temperature, washed, and dried to obtain the cathode roller; the passivation solution contains the following mass components: 2.5g / L ammonium titanate, 3.6g / L hexamethylenetetramine, and 0.070~0.075g / L diethanolamine.

[0058] Comparative Example 1: A processing technology for a large-size titanium-based cathode roller, comprising the following processes:

[0059] The billet is selected from industrial pure titanium TA1 with a height-to-diameter ratio of 2:1, and includes the following mass composition: iron: 0.21%, carbon: 0.013%, oxygen: 0.097%, nitrogen: 0.012%, hydrogen: 0.001%, other impurities <0.2%, and the balance is titanium;

[0060] Step 1: Take the billet and use a 6500T press to upset the billet until the height of the ring billet is 1.1 times the height of the ring piece; Punching: The diameter of the ring billet is 4 times the diameter of the punch. The ring billet is enlarged using a frame, and the inner diameter is 1.25 times the diameter of the mandrel of the vertical ring rolling mill; Mandrel lengthening is performed; End rolling: Asynchronous rolling is used to roll the ring billet 8 times, with a processing rate of 42%, to obtain the ring billet; The height of the ring billet is 1.1 times the height of the ring piece;

[0061] Step 2: Take the ring blank obtained in Step 1, grind it to remove damage, scribing and inspect it;

[0062] Step 3: Take the ring blank obtained in Step 2 and turn it to obtain the ring part;

[0063] Step 4: The ring obtained in Step 3 is subjected to heat treatment. The heat treatment process is: annealing at 200℃ for 20 min. Passivation treatment is performed as follows: 35g of titanium dioxide is placed in 1L of potassium hydroxide solution (10mol / L) and hydrothermally reacted at 210℃ for 24h; after cooling to room temperature, the precipitate is taken, washed with water until the pH of the system is 9, and placed in 1L of ammonium nitrate solution (0.1mol / L) and stirred for 4h. After centrifugation, the reaction is repeated several times, washed with water, and vacuum dried at 60℃ to obtain ammonium titanate; the ring obtained after heat treatment is placed in the passivation solution and hydrothermally reacted at 210℃ for 12h; after removal, it is cooled to room temperature, washed, and dried to obtain the cathode roller; the passivation solution contains the following mass components: 2.2g / L ammonium titanate, 3.4g / L hexamethylenetetramine, and 0.070g / L diethanolamine.

[0064] Comparative Example 2: A processing technology for a large-size titanium-based cathode roller, comprising the following processes:

[0065] The billet is selected from industrial pure titanium TA1 with a height-to-diameter ratio of 2:1, and includes the following mass composition: iron: 0.21%, carbon: 0.013%, oxygen: 0.097%, nitrogen: 0.012%, hydrogen: 0.001%, other impurities <0.2%, and the balance is titanium;

[0066] Step 1: Take the billet and use a 6500T press to upset the billet until the height of the ring billet is 1.1 times the height of the ring piece; Punching: The diameter of the ring billet is 4 times the diameter of the punch. The ring billet is enlarged using a frame, and the inner diameter is 1.25 times the diameter of the mandrel of the vertical ring rolling mill; The mandrel is then lengthened; End rolling: Asynchronous rolling is used to roll the ring billet 6 times, with a processing rate of 26%; Then synchronous rolling is used to roll the ring billet 2 times, with a processing rate of 22%. The speed ratio of the upper and lower rolls is 3:2 to obtain the ring billet; The height of the ring billet is 1.1 times the height of the ring piece;

[0067] Step 2: Take the ring blank obtained in Step 1, grind it to remove damage, scribing and inspect it;

[0068] Step 3: Take the ring blank obtained in Step 2 and turn it to obtain the ring part;

[0069] Step 4: The ring obtained in Step 3 is subjected to heat treatment. The heat treatment process is: annealing at 650℃ for 20 minutes. Passivation treatment is performed as follows: 35g of titanium dioxide is placed in 1L of potassium hydroxide solution (10mol / L) and hydrothermally reacted at 210℃ for 24 hours; after cooling to room temperature, the precipitate is taken, washed with water until the pH of the system is 9, and placed in 1L of ammonium nitrate solution (0.1mol / L) and stirred for 4 hours. After centrifugation, the reaction is repeated several times, washed with water, and vacuum dried at 60℃ to obtain ammonium titanate; the ring obtained after heat treatment is placed in the passivation solution and hydrothermally reacted at 210℃ for 12 hours; after removal, it is cooled to room temperature, washed, and dried to obtain the cathode roller; the passivation solution contains the following mass components: 2.2g / L ammonium titanate, 3.4g / L hexamethylenetetramine, and 0.070g / L diethanolamine.

[0070] Comparative Example 3: A processing technology for a large-size titanium-based cathode roller, comprising the following processes:

[0071] The billet is selected from industrial pure titanium TA1 with a height-to-diameter ratio of 2:1, and includes the following mass composition: iron: 0.21%, carbon: 0.013%, oxygen: 0.097%, nitrogen: 0.012%, hydrogen: 0.001%, other impurities <0.2%, and the balance is titanium;

[0072] Step 1: Take the billet and use a 6500T press to upset the billet until the height of the ring billet is 1.1 times the height of the ring piece; Punching: The diameter of the ring billet is 4 times the diameter of the punch. The ring billet is enlarged using a frame, and the inner diameter is 1.25 times the diameter of the mandrel of the vertical ring rolling mill; The mandrel is then lengthened; End rolling: Asynchronous rolling is used to roll the ring billet 6 times, with a processing rate of 26%; Then synchronous rolling is used to roll the ring billet 2 times, with a processing rate of 22%. The speed ratio of the upper and lower rolls is 3:2 to obtain the ring billet; The height of the ring billet is 1.1 times the height of the ring piece;

[0073] Step 2: Take the ring blank obtained in Step 1, grind it to remove damage, scribing and inspect it;

[0074] Step 3: Take the ring blank obtained in Step 2 and turn it to obtain the ring part;

[0075] Step 4: The ring obtained in Step 3 is subjected to heat treatment. The heat treatment process is: annealing at 200℃ for 20 minutes. Passivation treatment is then performed. The passivation treatment process is: the heat-treated ring is placed in a passivation solution and hydrothermally reacted at 210℃ for 12 hours; it is then removed, cooled to room temperature, washed, and dried to obtain the cathode roller; the passivation solution contains the following mass components: 2.0 g / L ammonium hexafluorotitanate and 1.32 g / L hydrofluoric acid.

[0076] The cathode rollers obtained in Examples 1-3 and Comparative Examples 1-3 were used to prepare samples, and their performance was tested and the test results were recorded:

[0077] Grain size rating: The average grain size of the sample was determined with reference to GB / T 6394-2017.

[0078] Mechanical properties: Tensile properties of the specimens were tested using a material testing machine at a strain rate of 1×10⁻⁶. -3 s -1 ;

[0079] Corrosion resistance: Electrochemical testing was conducted using a three-electrode system. A saturated calomel electrode was used as the reference electrode, a platinum electrode as the auxiliary electrode, and the sample was used as the working electrode. The electrolyte solution was 1.0 M sulfuric acid. The test results showed that the sample could withstand corrosion at 1.0 V. SCE The electrochemical impedance at 60℃ was measured.

[0080]

[0081] Based on the data in the table above, the following conclusions can be clearly drawn:

[0082] The cathode rollers obtained in Examples 1-3 are compared with those obtained in Comparative Examples 1-3. The test results show that...

[0083] Compared with the comparative examples, the cathode rollers obtained in Examples 1-3 have a higher grain size grade and a grain size dispersion of no more than 0.5 grade, as well as higher tensile strength and impedance data. This fully demonstrates that the present invention achieves improvements in the surface grain size, mechanical properties, and corrosion resistance of the cathode roller.

[0084] Compared with Example 1, the end rolling process in Comparative Example 1 is different, and only asynchronous rolling is used; the heat treatment temperature in Comparative Example 2 is higher, at 650°C; the passivation liquid composition in Comparative Example 3 is different; its grain size rating is significantly reduced, and the tensile strength and impedance data are reduced accordingly. It can be seen that the setting of the cathode roll process and the composition used in this invention can promote the improvement of the surface grain size, mechanical properties and corrosion resistance of the cathode roll, and meet its morphology and mechanical properties requirements at the microstructure level.

[0085] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process method article or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such a process method article or apparatus.

[0086] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, or 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 processing technology for a large-size titanium-based cathode roller, characterized in that: Including the following processes: Step 1: Take the billet and perform high-temperature upsetting and drawing, punching, hole enlargement, and mandrel drawing to obtain a ring billet; Step 2: Take the ring blank obtained in Step 1, grind it to remove damage, scribing and inspect it; Step 3: Take the ring blank obtained in Step 2 and turn it to obtain the ring part; Step 4: Take the ring obtained in Step 3 and perform post-processing to obtain the cathode roller; the post-processing in Step 4 includes heat treatment and passivation processes. The passivation process is as follows: the ring obtained after heat treatment is placed in a passivation solution and subjected to hydrothermal reaction at 210-230°C for 12-24 hours; then it is removed, cooled to room temperature, washed, and dried. The passivation solution contains the following components by mass: 2.2–2.5 g / L ammonium titanate, 3.4–3.6 g / L hexamethylenetetramine, and 0.070–0.075 g / L diethanolamine.

2. The processing technology for a large-size titanium-based cathode roller according to claim 1, characterized in that: The height of the ring blank is 1.1 times the height of the ring.

3. The processing technology for a large-size titanium-based cathode roller according to claim 1, characterized in that: After step one, the ring billet is subjected to end rolling, which specifically includes the following processes: Asynchronous rolling is used to roll the ring billet 6 to 9 times, with a processing rate of 26% to 36%; then synchronous rolling is used to roll the ring billet 2 to 3 times, with a processing rate of 22% to 25%.

4. The processing technology for a large-size titanium-based cathode roller according to claim 3, characterized in that: The upper and lower rolls in synchronous rolling have a rotational speed ratio of 3:

2.

5. The processing technology for a large-size titanium-based cathode roller according to claim 1, characterized in that: The heat treatment process is as follows: annealing at 200-400℃ for 20-30 minutes.

6. The processing technology for a large-size titanium-based cathode roller according to claim 1, characterized in that: The ammonium titanate is prepared by the following process: Titanium dioxide was placed in potassium hydroxide solution and hydrothermally reacted at 210–230 °C for 24 h. After cooling to room temperature, the precipitate was taken, washed with water, and placed in ammonium nitrate solution and stirred for 4–8 h. After centrifugation, the reaction was repeated several times, washed with water, and dried under vacuum at 60 °C.

7. A large-size titanium-based cathode roller manufactured using the processing technology described in any one of claims 1-6.

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