Cathode roller with honeycomb surface structure and method for manufacturing alloy foil by using cathode roller

Abstract

The invention discloses a cathode roller with a honeycomb surface structure. A precise honeycomb micro-pattern structure is arranged on the surface of the cathode roller. The invention also discloses a method for manufacturing alloy foil by using the cathode roller, which comprises the following steps: dissolving ferric salt in ultrapure water to obtain a ferric salt solution; dissolving nickel salt in ultrapure water to obtain a nickel salt solution; mixing the two solutions and filtering; preparing various additive solutions, mixing all the additive solutions with the obtained iron-nickel solution to obtain an electrolyte, filtering the electrolyte, and transferring the filtered electrolyte into an electrolytic cell of a crude foil engine; and applying current to a cathode roller and an anode plate which are separately arranged in the electrolytic bath, electrically depositing iron and nickel on the surface of the cathode roller, and rolling through a roll-to-roll process to obtain the iron-nickel alloy foil. The alloy foil manufactured by the method has the characteristics of low surface roughness, high tensile strength and high ductility.

Description

Technical Field

[0001] The present invention belongs to the technical field of alloy foil manufacturing methods, and relates to a cathode roller with a honeycomb surface structure. The present invention also relates to a method for manufacturing alloy foil using this cathode roller. Background Art

[0002] Iron-nickel alloy is a metallic material that can simultaneously achieve functional characteristics such as precise control of the coefficient of thermal expansion, excellent magnetic properties, high mechanical strength, and excellent corrosion resistance. It is widely used in various industrial fields with strict requirements for reliability and durability. In particular, iron-nickel alloy in the form of metal foil plays an important role in high-functional application scenarios such as semiconductor lead frames, high-density circuit boards, electromagnetic shielding materials, precision sensors, secondary battery components, aerospace components, and medical electronic devices.

[0003] In recent years, with the accelerated development of various cutting-edge industries such as the precision of semiconductor processes, the high-speed development of AI computing technology, the commercialization of 6G high-frequency communication, the high reliability of automotive electronic components, and the lightweight of precision medical sensors, the performance requirements for metal foils used in electronic devices and high-frequency circuits have also evolved towards ultra-precision and high-end. Specifically, in the field of semiconductor packaging, extremely high surface flatness is required; in the fields of AI and 6G communication, to achieve low signal loss, ultra-low roughness surface characteristics are required; while electromagnetic shielding materials need to construct a precise pattern structure that can achieve frequency-selective reflection or absorption. Most of the iron-nickel alloy foils used for the above applications are manufactured by electroplating processes, and the rotating cathode roller used therein is the core equipment that determines key indicators such as the surface quality, roughness, grain structure, and thickness uniformity of the metal foil. During electroplating, when metal ions reach the surface of the cathode roller, they grow in the form of a thin film. At this time, the state formed on the surface of the cathode roller will directly affect the initial surface state of the metal foil. Therefore, the surface structure of the cathode roller has transcended the category of a simple physical mold and has become a key factor determining the functional characteristics of the foil and its compatibility with subsequent processes. Due to the lack of specific structural features on the surface of the flat cathode roller, the deposition of metal ions during electroplating will be affected by uneven surface current distribution, resulting in problems such as local thickness deviation, uneven grains, and roughness differences in the coating. Over-deposition occurs in the current concentration area, while insufficient deposition occurs in the current dispersion area. This phenomenon will significantly affect the thickness uniformity and surface roughness of the coating.

[0004] In addition, when the electrode surface lacks functional structures due to a simple planar configuration, the metal ion flow will be randomly distributed uncontrollably, resulting in differences in the grain growth orientation and size with changes in position. This non-uniformity will have a negative impact on the overall mechanical properties of the alloy foil. Especially in high-end application fields that require high-speed signal transmission or precision pattern forming, it may cause a series of problems such as electrical losses, poor contact, and electromagnetic wave leakage. In addition, when the surface roughness is unevenly distributed, it will also have a negative impact on the bonding characteristics, contact resistance, and electrical conductivity reliability in subsequent processes, making it difficult to meet the requirements of high-performance alloy foil materials. It can be seen that the traditional process using a simple planar cathode roll has limitations - it cannot precisely adjust the current distribution and grain growth during electroplating, resulting in difficulties in ensuring process accuracy in multiple quality indicators such as the roughness, mechanical strength, and electrical characteristics of the metal foil. To break through these technical bottlenecks, an innovative cathode roll technology needs to be developed - by constructing precise repetitive structures on the surface of the cathode roll, achieving uniform current distribution, stabilizing the metal ion flow, and controllable grain growth. Summary of the Invention

[0005] The object of the present invention is to provide a cathode roll with a honeycomb surface structure for manufacturing alloy foil, which has the characteristics of improving the current uniformity during electrodeposition and thus reducing the surface roughness of the manufactured alloy foil.

[0006] Another object of the present invention is to provide a method for manufacturing alloy foil using the above cathode roll, and the manufactured alloy foil has the characteristics of low surface roughness, high tensile strength, and high elongation.

[0007] The technical solution adopted by the present invention is that for the cathode roll with a honeycomb surface structure, a precise honeycomb micro-pattern structure is provided on the surface of the cathode roll, and this structure is formed by an array of regular hexagon patterns with a side length of 10 μm and a depth of 2.5 μm, and the distance between adjacent hexagons is 5 μm.

[0008] Another technical solution adopted by the present invention is a method for manufacturing alloy foil using a cathode roll with a honeycomb surface structure, which is specifically implemented according to the following steps: Step 1: Dissolve iron salt in ultrapure water to obtain an iron salt solution; dissolve nickel salt in ultrapure water to obtain a nickel salt solution; mix the two solutions and filter. Step 2: Prepare various additive solutions, mix all the additive solutions with the solution obtained in Step 1 to obtain an electrolyte solution, filter the electrolyte solution and transfer it to the electrolytic cell of the raw foil machine. Step 3: Apply current to the separately arranged cathode roll and anode plate in the electrolytic cell, electro-deposit iron and nickel on the surface of the cathode roll, and wind it up through a roll-to-roll process to obtain an iron-nickel alloy foil.

[0009] The characteristics of another technical solution of the present invention also lie in: In Step 1, the iron salt is ferrous sulfate or ferrous chloride, and the nickel salt is nickel carbonate, nickel sulfate or nickel chloride.

[0010] In the electrolyte obtained in Step 2, the concentration of iron ions is 25 - 115 g / L; the concentration of nickel ions is 12 - 45 g / L.

[0011] The additives include an iron reducing agent, a pH stabilizer, a conductive aid, a stress reliever, a tensile strength enhancer and an elongation enhancer.

[0012] The iron reducing agent is citric acid, ascorbic acid or nitrilotriacetic acid, and its addition amount is 1.0 - 12.0 g / L; The pH stabilizer is boric acid, formic acid or acetic acid, and its addition amount is 3.0 - 15.0 g / L; The conductive aid is ammonium chloride, sodium sulfate or potassium chloride, and its addition amount is 10.0 - 30.0 g / L; The stress reliever is sodium saccharin, sodium benzoate or benzotriazole, and its addition amount is 0.05 - 1.0 g / L.

[0013] The tensile strength enhancer is zinc gluconate, and its addition amount is 0.05 - 0.5 g / L; the elongation enhancer is malic acid, and its addition amount is 1.0 - 10.0 g / L.

[0014] During the electro - deposition process in Step 3, the electrolyte temperature is 40 - 60 °C, the current density is 10 - 35 A / dm², the electrolyte flow rate is 20 - 50 m 3 / hr, and the pH value of the electrolyte is 2.0 - 3.0.

[0015] The beneficial effects of the present invention are as follows: (1) On the surface of the cathode roller of the present invention, there is a precision honeycomb - shaped micro - pattern structure, which is formed by an array of regular hexagon patterns with a side length of 10 μm and a depth of 2.5 μm, and the distance between two adjacent hexagons is 5 μm. This structure can effectively regulate the current distribution during electroplating, and by preventing local current concentration, it can structurally suppress problems such as thickness deviation, unevenness and surface defects of the deposition layer. The results show that the foil can achieve an ultra - low roughness characteristic at the level of 0.10 - 0.15 μm for surface roughness (Ra), and the coating grains are uniform and fine, synchronously improving the mechanical strength and electrical reliability of the alloy foil; (2) In the method of the present invention, a tensile strength enhancer (additive E) and an elongation enhancer (additive F) are added to the electrolyte under the optimal conditions. Among them, additive E (zinc gluconate) passes through trace zinc ions (Zn 2+The function of () can promote the densification and homogenization of metal grains, thus significantly improving the tensile strength of the deposited layer (reaching about 1400 - 1600 MPa level); Additive F (malic acid) can stably ensure the elongation rate (4.0 - 6.0%) of the deposited layer by regulating the grain growth rate and inducing the formation of a flexible crystal structure. In addition to their respective independent effects, these two additives can, through multiple synergistic effects such as current distribution regulation, grain growth optimization, and stress dispersion, go beyond the simple improvement of surface roughness and achieve the simultaneous improvement of overall performance balance and process stability; (3) Through the dual optimization of the cathode roll structure and the electrolyte additive formula, the method of the present invention has achieved a breakthrough improvement in mechanical properties, fundamentally overcoming the inherent technical limitations such as surface unevenness, weakening of mechanical properties, and defect generation existing in the traditional planar cathode roll structure and conventional electrolyte ratio technology. Therefore, the iron-nickel alloy foil manufactured by the method of the present invention can be applied to cutting-edge industrial fields such as AI semiconductor circuit boards, 6G high-frequency communication modules, and ultra-precision sensor electronic materials that require both high functionality and high reliability. As a core material that simultaneously meets the characteristics of low roughness, high strength, and high ductility, it can continuously maintain excellent quality in a high-speed signal transmission environment that requires long-term performance stability and structural precision, providing technical competitiveness. Brief Description of the Drawings

[0016] Figure 1 is a schematic structural diagram of the cathode roll with a honeycomb surface structure of the present invention; Figure 2 is an SEM image of the alloy foil prepared in Example 1 of the present invention; Figure 3 is an SEM image of the alloy foil prepared in Comparative Example 1 of the present invention. Detailed Description of the Invention

[0017] The present invention will be described in detail below with reference to the drawings and specific embodiments.

[0018] The structure of the cathode roll with a honeycomb surface structure of the present invention is as Figure 1 shown. The surface of the cathode roll is provided with a precise honeycomb micro-pattern structure, which is formed by an array of regular hexagon patterns with a side length of 10 μm and a depth of 2.5 μm, and the distance between adjacent hexagons is 5 μm. This pattern structure is prepared by a high-precision lithography process or a precision mold processing technology, and has the durability and shape accuracy characteristics that can be directly applied to the electroplating process.

[0019] The method for manufacturing alloy foil using a cathode roller with a honeycomb surface structure according to the present invention is as follows: First, for preparing the electrolyte for alloy foil, ferric salt and ultrapure water are put into a dissolution tank through a first metering supply device for dissolution and stirring; nickel salt and ultrapure water are put into a waste liquid tank through a second metering supply device for dissolution and stirring. After the two dissolved solutions are circulated and mixed, impurities are removed through a diatomite filter and moved to a clean liquid tank. In addition, for stable preparation of alloy foil, various additives (including special additives for improving mechanical properties) are respectively dissolved and stirred with ultrapure water in respective additive tanks and then moved to the clean liquid tank. The iron-nickel electrolyte mixed with additives in the clean liquid tank is filtered through a fine filter and then moved to the electrolytic cell of a foil making machine. An electric current is applied to the electrolytic cell filled with the electrolyte (a cathode roller and an anode plate are arranged in the electrolytic cell), so that the alloy foil is deposited on the surface of the cathode roller, and finally the manufacturing is completed by winding through a roll-to-roll process.

[0020] The core technology of the method of the present invention lies in: by using a cathode roller with a hexagonal (honeycomb) surface structure, the surface characteristics, crystal structure and mechanical properties of the iron-nickel alloy foil are fundamentally improved. Due to the lack of high-precision surface control technology in traditional cathode rollers, irregular and unpredictable concave and convex structures will be formed on their surfaces. Such non-ideal surfaces will cause local distortion of the current distribution and lead to uneven grain growth and roughness deviation of the deposition layer during the electroplating process, resulting in the inability to control the quality stability and precision of the metal foil.

[0021] The hexagonal (honeycomb) surface structure cathode roll of the present invention can evenly disperse the current across the entire surface of the cathode roll during electroplating and stabilize the diffusion of metal ions, thereby improving the uniformity of the deposition layer and the stability of surface roughness, enhancing the grain control effect. It can not only effectively ensure a low surface roughness but also have a positive impact on improving the tensile strength and elongation of the metal foil by stabilizing the formation of grains during the initial deposition. The hexagonal grid structure is an optimized shape that minimizes interference between adjacent units while evenly dispersing the electric field distribution, fundamentally suppressing the occurrence of deposition defects such as local protrusions, depressions, and uneven thickness that may be caused by current concentration. This current stability enables the growth orientation and size of metal grains to remain uniform, resulting in the produced iron-nickel alloy foil having surface flatness, uniform fine grain size, and consistent electrical properties. In addition, this regular crystal structure is conducive to the dispersion of the overall mechanical stress of the metal foil, preventing local fracture and stress concentration during the stretching process, thereby improving both the tensile strength and elongation simultaneously. At the same time, the high-precision repeatability of the hexagonal pattern not only reduces the surface roughness but also plays a key role in the overall structural stability and functional control characteristics of the coating. During the electroplating process, the flow of metal ions in the electrolyte is regulated by the pattern structure, enabling the uniform formation of the orientation and density of fine grains in the deposition layer. This characteristic constitutes a key performance basis particularly in application fields that require precise electrical properties such as high-frequency signal transmission characteristics or signal loss suppression in high-density circuit boards.

[0022] In addition, the design of the cathode roll of the present invention retains compatibility with existing electroplating process equipment. Only by replacing the cathode roll can the production of high-performance iron-nickel alloy foil be immediately achieved without additional equipment modification. Its hexagonal structure has excellent mechanical stress dispersion characteristics, which can simultaneously ensure the durability and long-term operation stability of the cathode roll itself, while demonstrating excellent pattern retention ability and quality reproducibility. Therefore, the hexagonal pattern cathode roll provided by the present invention fundamentally overcomes the structural technical limitations of traditional flat structure cathode rolls, such as uneven roughness, unstable grain growth, and current deviation. Through a precise and reusable surface pattern structure, it has become an optimized solution for manufacturing iron-nickel alloy foil with high functionality, high reliability, and high mechanical properties.

[0023] The electrolyte used for the manufacture of the above alloy foil is a solution containing iron-nickel components and various additives, and its specific composition is as follows: The mass percentages of each metal in the iron-nickel alloy foil are: iron 45 - 85% and nickel 15 - 55%.

[0024] The electrolyte is composed of iron salts, nickel salts and various additives. Among them, the concentration of iron ions is 25 - 115 g / L, and the concentration of nickel ions is 12 - 45 g / L. The iron salts can be ferrous sulfate or ferrous chloride, and the nickel salts can be nickel carbonate, nickel sulfate or nickel chloride. The temperature of the electrolyte is maintained at 40 - 60 °C, the current density is 10 - 35 A / dm², the flow rate is 20 - 50 m 3 / hr, and the pH value is maintained at 2.0 - 3.0, and sulfuric acid and sodium carbonate are used to control the pH value within the specified range.

[0025] The electrolyte used in the method of the present invention contains functional additives, including an iron reducing agent (additive A), a pH stabilizer (additive B), a conductive aid (additive C), a stress reliever (additive D), a tensile strength enhancer (additive E) and an elongation enhancer (additive F). Each additive must be added within the specified range to fully exert its effect.

[0026] Among them, the iron reducing agent (additive A) used is citric acid, ascorbic acid or nitrilotriacetic acid, and its addition amount is 1.0 - 12.0 g / L, which plays a role in inhibiting the oxidation of iron ions (Fe 2+ ). When the addition amount is less than 1.0 g / L, the oxidation of Fe 2+ cannot be effectively prevented, resulting in the conversion of Fe 2+ in the solution into trivalent iron ions (Fe 3+ ) and the formation of precipitates, which may cause coating defects. When the addition amount exceeds 12.0 g / L, the reduction effect will reach the saturation state, which not only cannot further improve the performance, but may also lead to unnecessary consumption of additives and imbalance of the electrolyte ion balance.

[0027] The pH stabilizer (additive B) used is boric acid, formic acid or acetic acid, and its addition amount is 3.0 - 15.0 g / L, which plays a role in maintaining the stability of the acidity (pH value) of the electrolyte. When the addition amount is less than 3.0 g / L, the pH value fluctuation range will expand due to insufficient stabilization ability. This instability may destroy the balanced environment for grain growth, thereby inducing the formation of microdefects inside the alloy foil. On the contrary, when the addition amount exceeds 15.0 g / L, it will exceed the effective range of the stabilizing effect, resulting in side effects such as abnormal increase in conductivity and salt accumulation, thus seriously affecting the precise control of the deposition reaction.

[0028] The conductive aid (Additive C) used is ammonium chloride, sodium sulfate, or potassium chloride, and its addition amount is 10.0 - 30.0 g / L, which plays a role in stabilizing the current flow in the electroplating process. When the addition amount is less than 10.0 g / L, the resistance of the electrolyte will increase, resulting in uneven current distribution, and thus may cause fluctuations in the thickness of the foil. On the contrary, if the addition amount exceeds 30.0 g / L, it may lead to hindered diffusion of metal ions due to excessive accumulation of ions in the electrolyte, and cause surface scars or particle agglomeration.

[0029] The stress reliever (Additive D) used is sodium saccharin, sodium benzoate, or benzotriazole, and its addition amount is 0.05 - 1.0 g / L, which plays a role in refining the crystal grains and reducing the deposition stress. When the addition amount is less than 0.05 g / L, the stress relief effect is insufficient, which may cause residual stress and peeling phenomenon in the coating. On the contrary, if the addition amount exceeds 1.0 g / L, it may lead to a decrease in the reaction activity of metal ions and a reduction in current efficiency, and at the same time will overly inhibit the growth of crystal grains, resulting in over-dense or non-uniform coating.

[0030] The tensile strength enhancer (Additive E) used is zinc gluconate, and its addition amount is 0.05 - 0.5 g / L. By introducing trace zinc ions (Zn 2+ ), it promotes the formation of a dense crystal structure, thereby enhancing the tensile strength. When the addition amount is less than 0.05 g / L, the strengthening effect of zinc is insufficient, which not only cannot significantly improve the mechanical properties, but may instead increase the pinhole defects. On the contrary, when the addition amount exceeds 0.5 g / L, the infiltration of excessive zinc ions (Zn 2+ ) will cause uneven crystal grains and stress concentration, which will instead reduce the tensile strength and may cause roughening of the coating surface.

[0031] The elongation enhancer (Additive F) used is malic acid, and its addition amount is 1.0 - 10.0 g / L. By delaying the crystal grain growth rate, it induces the formation of a flexible crystal structure. When the addition amount is less than 1.0 g / L, it will be difficult to ensure the ductility of the material, resulting in a decline in mechanical elongation characteristics, and may cause crack defects due to local stress concentration. On the contrary, when the addition amount exceeds 10.0 g / L, the crystal structure will be overly loosened, which may lead to simultaneous deterioration of the mechanical strength and surface quality of the coating.

[0032] The thickness of the iron-nickel alloy foil prepared by the method of the present invention is 8 um, which has ultra-precise surface roughness, uniform crystal grain structure, and excellent tensile strength and elongation. It is a highly functional foil material that can be widely applied to new-generation industrial fields such as AI semiconductor circuit boards, high-frequency communication electronic materials, and precision sensor substrates that require comprehensive mechanical properties and electrical characteristics.

[0033] Example 1: An electric current is applied to an electrolytic cell filled with electrolyte, causing alloy foil to deposit on the surface of a cathode roll with a hexagonal micro-patterned structure. Finally, the manufacturing is completed by winding through a roll-to-roll process. The iron salt added to the electrolyte is ferrous sulfate, and the nickel salt is nickel sulfate. The concentration of iron ions is 90.0 g / L, and the concentration of nickel ions is 40.0 g / L. The electrolyte temperature is maintained at 45 °C, the current density is 15 A / dm², the flow rate is 25 m 3 / hr, and the pH value is maintained at 2.5. The additives are added in the following ratios: Iron reducing agent (additive A): Citric acid 4.0 g / L pH stabilizer (additive B): Boric acid 6.0 g / L Conductive aid (additive C): Ammonium chloride 10.0 g / L Stress reliever (additive D): Sodium saccharin 0.1 g / L Tensile strength enhancer (additive E): Zinc gluconate 0.05 g / L Elongation enhancer (additive F): Malic acid 1.0 g / L Example 2: A cathode roll with a hexagonal micro-patterned structure is used, and ferrous chloride is used as the iron salt, and nickel chloride is used as the nickel salt. The concentration of iron ions is 100 g / L, the concentration of nickel ions is 45 g / L, the electrolyte temperature is maintained at 48 °C, the current density is 20 A / dm², the flow rate is 30 m 3 / hr, and the pH value is maintained at 2.5. The additives are added in the following ratios: Iron reducing agent (additive A): Ascorbic acid 5.5 g / L pH stabilizer (additive B): Acetic acid 9.0 g / L Conductive aid (additive C): Sodium sulfate 15.0 g / L Stress reliever (additive D): Benzotriazole 0.2 g / L Tensile strength enhancer (additive E): Zinc gluconate 0.10 g / L Elongation enhancer (additive F): Malic acid 3.0 g / L Example 3 A cathode roll with a hexagonal micro-patterned structure is used, and ferrous sulfate is used as the iron salt, and nickel carbonate is used as the nickel salt. The concentration of iron ions is 85 g / L, the concentration of nickel ions is 38 g / L, the electrolyte temperature is maintained at 50 °C, the current density is 25 A / dm², the flow rate is 35 m 3 / hr, and the pH value is maintained at 2.5. The additives are added in the following ratios: Iron reducing agent (additive A): Citric acid 6.0 g / L pH stabilizer (additive B): Boric acid 12.0 g / L Conductive aid (Additive C): Ammonium chloride 20.0 g / L Stress reliever (Additive D): Sodium benzoate 0.3 g / L Tensile strength enhancer (Additive E): Zinc gluconate 0.15 g / L Elongation enhancer (Additive F): Malic acid 5.0 g / L Example 4 A cathode roll with a hexagonal micro-pattern structure is used, and ferrous chloride is used as the iron salt and nickel sulfate is used as the nickel salt. The iron ion concentration is 95 g / L, the nickel ion concentration is 42 g / L, the electrolyte temperature is maintained at 52 °C, the current density is 28 A / dm², the flow rate is 40 m 3 / hr, and the pH value is maintained at 2.5. The additives are added in the following ratios: Iron reducing agent (Additive A): Nitrilotriacetic acid 7.0 g / L pH stabilizer (Additive B): Formic acid 15.0 g / L Conductive aid (Additive C): Potassium chloride 25.0 g / L Stress reliever (Additive D): Sodium benzoate 0.4 g / L Tensile strength enhancer (Additive E): Zinc gluconate 0.20 g / L Elongation enhancer (Additive F): Malic acid 6.0 g / L Example 5: A cathode roll with a hexagonal micro-pattern structure is used, and ferrous sulfate is used as the iron salt and nickel chloride is used as the nickel salt. The iron ion concentration is 105 g / L, the nickel ion concentration is 36 g / L, the electrolyte temperature is maintained at 55 °C, the current density is 30 A / dm², the flow rate is 45 m 3 / hr, and the pH value is maintained at 2.5. The additives are added in the following ratios: Iron reducing agent (Additive A): Nitrilotriacetic acid 8.0 g / L pH stabilizer (Additive B): Acetic acid 4.0 g / L Conductive aid (Additive C): Sodium sulfate 30.0 g / L Stress reliever (Additive D): Sodium saccharin 0.5 g / L Tensile strength enhancer (Additive E): Zinc gluconate 0.25 g / L Elongation enhancer (Additive F): Malic acid 8.0 g / L Example 6: A cathode roll with a hexagonal micro-pattern structure is used, and ferrous chloride is used as the iron salt and nickel carbonate is used as the nickel salt. The iron ion concentration is 110 g / L, the nickel ion concentration is 39 g / L, the electrolyte temperature is maintained at 57 °C, the current density is 35 A / dm², the flow rate is 50 m3 / hr, and the pH value is maintained at 2.5. The additives are added according to the following ratios: Iron reducing agent (Additive A): Citric acid 9.0 g / L pH stabilizer (Additive B): Boric acid 8.0 g / L Conductive aid (Additive C): Ammonium chloride 18.0 g / L Stress reliever (Additive D): Benzotriazole 0.6 g / L Tensile strength enhancer (Additive E): Zinc gluconate 0.30 g / L Elongation enhancer (Additive F): Malic acid 10.0 g / L Comparative Example 1: This comparative example is basically the same as Example 1, except that a conventional planar cathode roller is used.

[0034] Comparative Example 2: This comparative example is basically the same as Example 2, except that a conventional planar cathode roller is used.

[0035] Comparative Example 3: This comparative example is basically the same as Example 3, except that a conventional planar cathode roller is used.

[0036] Comparative Example 4: This comparative example is basically the same as Example 4, except that the tensile strength enhancer (Additive E) and the elongation enhancer (Additive F) are not added.

[0037] Comparative Example 5: This comparative example is basically the same as Example 4, except that a small amount of the tensile strength enhancer (Additive E) and the elongation enhancer (Additive F) are added, and the additives are added according to the following ratios: Iron reducing agent (Additive A): Nitrilotriacetic acid 7.0 g / L pH stabilizer (Additive B): Formic acid 15.0 g / L Conductive aid (Additive C): Potassium chloride 25.0 g / L Stress reliever (Additive D): Sodium benzoate 0.4 g / L Tensile strength enhancer (Additive E): Zinc gluconate 0.01 g / L Elongation enhancer (Additive F): Malic acid 0.5 g / L Comparative Example 6: This comparative example is basically the same as Example 5, except that the elongation enhancer (Additive F) is not added.

[0038] Comparative Example 7: This comparative example is basically the same as Example 5, except that the tensile strength enhancer (Additive E) is not added.

[0039] Comparative Example 8: This comparative example is basically the same as Example 6, except that the tensile strength enhancer (Additive E) and the elongation enhancer (Additive F) are added in excess, and each additive is added according to the following ratio: Iron reducing agent (Additive A): Citric acid 9.0 g / L pH stabilizer (Additive B): Boric acid 8.0 g / L Conductive aid (Additive C): Ammonium chloride 18.0 g / L Stress reliever (Additive D): Benzotriazole 0.6 g / L Tensile strength enhancer (Additive E): Zinc gluconate 0.60 g / L Elongation enhancer (Additive F): Malic acid 12.0 g / L Table 1 lists the types and contents of additives used in Examples 1-6 and Comparative Examples 1-8 of the present invention, as well as the cathode roll structure. The thickness, surface roughness (Ra), tensile strength at room temperature, and elongation at room temperature of the alloy foils prepared in each case were tested, and the results are shown in Table 2.

[0040] Table 1 Types and Contents of Additives Used in Each Case and Cathode Roll Structure

[0041] Table 2 Performance Test Results of Alloy Foils Prepared in Each Case

[0042] As can be seen from Table 1 and Table 2, the technical effects of the method of the present invention have been clearly manifested. In the electroplating process of iron-nickel alloy foil, in order to simultaneously achieve the stabilization of the surface roughness of the deposited layer and the improvement of mechanical properties (tensile strength and elongation), a cathode roll structure with a hexagonal micro-pattern structure and a combination of functional additives E and F are used as the core technical means. In Examples 1 to 6, the concentrations of iron and nickel in the electrolyte, process conditions (temperature, current density, flow rate), and additives A to F are kept in a balanced ratio within a reasonable range. Especially when the tensile strength enhancer E and the elongation enhancer F are added simultaneously, the alloy foils prepared have a low surface roughness (Ra) of 0.10 - 0.15 μm at a thickness of 8 μm, and exhibit excellent mechanical properties: the tensile strength at room temperature reaches 1400 - 1600 MPa, and the elongation at room temperature is 4.0 - 6.0%. This technical effect stems from the synergistic effect of the hexagonal micro-pattern structure on the uniform regulation of current distribution (reducing surface roughness), additive E promoting grain densification and tissue homogenization (enhancing tensile strength), and additive F regulating the grain growth rate to generate a flexible crystal structure (improving elongation).

[0043] On the contrary, in Comparative Examples 1 - 8, either a planar cathode roll structure is adopted, or there is a situation where additives E / F are not added, added in trace amounts, or added in excess, and their surface roughness (Ra) and mechanical properties are significantly deteriorated compared with the examples. Among them, in Comparative Examples 1 - 3, by replacing the hexagonal micro-pattern structure cathode roll with a planar cathode roll, their surface roughness and tensile strength are lower than those of the corresponding Examples 1 - 3, fully proving that the regulation of current distribution by the hexagonal micro-pattern structure is the core factor for improving the coating quality. In addition, although Comparative Examples 4 - 8 adopt the hexagonal micro-pattern structure cathode roll, due to the non-addition or improper addition amount (trace or excess) of additives E and F, the performance deterioration phenomenon is significant. This result shows that when the addition amounts of additives E and F are within the optimal range, the arrangement of the coating structure and the stress dispersion effect can reach the best, so as to achieve the synergistic improvement of tensile strength and elongation.

[0044] In addition, Figure 2 is the SEM image of the alloy foil prepared in Example 1, Figure 3 is the SEM image of the alloy foil prepared in Comparative Example 1. It can be seen that under the same manufacturing process, the surface roughness of the alloy foil manufactured using the cathode roll with a honeycomb surface structure is much lower than that of the alloy foil manufactured using the planar cathode roll, which once again proves the role of the honeycomb surface structure cathode roll of the present invention in improving current uniformity and reducing the surface roughness of the alloy foil.

[0045] Based on the above experimental results, it has been clearly demonstrated that only by simultaneously applying the core technology of the present invention - the hexagonal micro-patterned cathode roller, and strictly controlling the dosages of additives E and F within the optimal range, can the ultra-low roughness, high tensile strength, and high elongation characteristics of iron-nickel alloy foils be achieved synchronously. This technology demonstrates the technical advantages and application potential as a core material in the fields of the new generation of semiconductor circuit boards, 6G communication modules, and high-precision sensor electronic materials that emphasize both high-frequency signal transmission, high-density integration, and mechanical durability. Through its technical foundation of high reliability and high functionality, it provides a new generation of electroplating technology solutions to meet the future industrial demands, and has significant technical value.

Claims

1. Honeycomb surface structure cathode roller, characterized in that: The surface of the cathode roller is provided with a precise honeycomb micro-pattern structure, which is composed of a regular hexagonal pattern array with a side length of 10 μm and a depth of 2.5 μm, and the spacing between adjacent hexagons is 5 μm.

2. A method for manufacturing alloy foil using a cathode roller with a honeycomb surface structure, characterized in that: Using the cathode roller as claimed in claim 1, the method is specifically implemented according to the following steps: Step 1, dissolving an iron salt in ultrapure water to obtain an iron salt solution; dissolving a nickel salt in ultrapure water to obtain a nickel salt solution; mixing the two solutions and filtering; Step 2, preparing various additive solutions, mixing all additive solutions with the solution obtained in step 1 to obtain an electrolyte, filtering the electrolyte and transferring it to the electrolytic cell of the foil machine; Step 3: applying current to the cathode roller and anode plate separately arranged in the electrolytic cell to electrodeposit iron and nickel on the surface of the cathode roller, and winding the roller by a roll-to-roll process to obtain an iron-nickel alloy foil.

3. The method for manufacturing alloy foil using a cathode roller with a honeycomb surface structure according to claim 2, characterized in that: In step 1, the iron salt is ferrous sulfate or ferrous chloride, and the nickel salt is nickel carbonate, nickel sulfate or nickel chloride.

4. The method for manufacturing alloy foil using a cathode roller with a honeycomb surface structure according to claim 2, characterized in that: In the electrolyte obtained in step 2, the iron ion concentration is 25-115 g / L; the nickel ion concentration is 12-45 g / L.

5. The method for manufacturing alloy foil using a cathode roller with a honeycomb surface structure according to claim 2, characterized in that: The additives include an iron reducing agent, a pH stabilizer, a conductive additive, a stress relaxant, a tensile strength enhancer and an elongation enhancer.

6. The method for manufacturing alloy foil using a cathode roller with a honeycomb surface structure according to claim 5, characterized in that: The iron reducing agent is citric acid, ascorbic acid or nitrilotriacetic acid, and the addition amount thereof is 1.0-12.0 g / L; The pH stabilizer is boric acid, formic acid or acetic acid, and the addition amount thereof is 3.0-15.0 g / L; The conductive additive is ammonium chloride, sodium sulfate or potassium chloride, and the addition amount thereof is 10.0-30.0 g / L; The stress reliever is sodium saccharin, sodium benzoate or benzotriazole, and the added amount thereof is 0.05-1.0 g / L.

7. The method for manufacturing alloy foil using a cathode roller with a honeycomb surface structure according to claim 5, characterized in that: The tensile strength enhancer is zinc gluconate, and its addition amount is 0.05-0.5 g / L; the elongation enhancer is malic acid, and its addition amount is 1.0-10.0 g / L.

8. The method for manufacturing alloy foil using a cathode roller with a honeycomb surface structure according to claim 2, characterized in that: During the electrodeposition process of step 3, the electrolyte temperature is 40-60°C, the current density is 10-35A / dm², and the electrolyte flow rate is 20-50m 3 / hr, the electrolyte pH is 2.0-3.0.

Images