Metal substrate device with functionalized surface modified by nanorods and preparation method of metal substrate device
By cleaning, thickening the oxide layer, and acid etching the metal substrate, an ordered array of nanopillars is formed, which solves the problems of high cost of laser ablation and slow rate of wet etching in the existing technology, and realizes low-cost and high-efficiency surface modification, which is suitable for mass production.
Patent Information
- Application Number
- CN202511727669.5
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-11-24
- Publication Date
- 2026-03-03
AI Technical Summary
In the design and structural modification of surface morphology of metal devices, existing technologies such as laser ablation are costly and complex to operate, while wet etching is slow and produces disordered modified surfaces, making it difficult to achieve efficient, fast and low-cost surface morphology design and structural modification.
By cleaning, thickening the oxide layer, and acid etching the metal substrate, an ordered array of nanopillars is formed on the surface of the metal substrate using an acidic solution of a specific concentration. The process includes cleaning, oxidation, and acid etching steps, controlling the oxide layer thickening and etching time, and employing a multi-step ultrasonic cleaning process to ensure the cleanliness of the device surface.
The prepared nanopillar-modified functionalized surface exhibits good dispersibility and uniformity, consistent surface morphology and size, is simple and efficient, suitable for large-scale production, and has low cost, thus possessing significant economic advantages.
Smart Images
Figure CN121592983A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of surface treatment technology for metal substrate devices, and in particular to a metal substrate device with a nanopillar-modified functionalized surface and its preparation method. Background Technology
[0002] With the continuous development of energy storage and conversion technologies, the demand for surface morphology design and structural modification of metal devices is increasing. In energy storage and conversion devices, metals and their alloys are key materials, and their surface morphology, structure, and properties have a decisive impact on the overall performance of the equipment. By increasing the surface roughness of metal devices and preparing ordered nanostructures, the number of reaction sites can be significantly increased, thereby improving the efficiency and performance of energy storage and conversion devices.
[0003] Currently, in the field of surface morphology design and structural modification of metal devices, laser ablation and wet etching are two commonly used surface morphology design techniques, which aim to increase the surface roughness of metal devices to expose more reaction sites.
[0004] Laser ablation is a method that uses a high-energy laser beam to ablate metal surfaces, creating complex microstructures that increase surface roughness and expose more reaction sites. This technology offers significant advantages in surface morphology design and structural modification of metal devices. However, laser ablation is costly, primarily due to the high price of the laser equipment and the need for specific environmental conditions, such as vacuum or inert gas protection to prevent oxidation or other adverse reactions. This increases operational complexity and cost, limiting its application in large-scale and commercial production.
[0005] Wet etching, as a more economical and simpler method, uses chemical reagents to etch metal surfaces to achieve morphology design and structural modification. Wet etching does not require expensive equipment, and the process is relatively simple and low-cost, making it suitable for large-scale production. However, this technology also has some limitations, such as a slower etching rate; furthermore, the selectivity of wet etching may not be as good as laser ablation, and the resulting modified surfaces are often rough and disordered structures.
[0006] Therefore, how to achieve these surface morphology designs and structural modifications in an efficient, rapid, and low-cost manner remains a key issue that urgently needs to be addressed in current research. Summary of the Invention
[0007] The main objective of this invention is to provide a metal substrate device with a nanopillar-modified functionalized surface and a method for its fabrication, so as to overcome the above-mentioned technical problems.
[0008] To achieve the above objectives, the present invention provides a method for fabricating a metal substrate device with a nanopillar-modified functionalized surface, comprising the following steps: S1 provides a cleaned metal substrate A; S2, in an oxygen-containing atmosphere, the metal substrate A is heated to a set temperature at a heating rate of 1~10℃ / min within a preset heating time, and held at that temperature for 10~300 minutes to obtain a metal substrate B with a thickened oxide layer. S3, the metal substrate B is acid-etched in an acidic solution of 0.1% to 50% w / w at a temperature of 25 to 100°C to obtain the metal substrate C; S4. The metal substrate C obtained by acid etching in step S3 is cleaned with anhydrous ethanol and dried to obtain a metal substrate device with a nanopillar-modified functional surface.
[0009] Preferably, in step S1, the thickness of the metal substrate A is 100nm~10mm, and the material of the metal substrate A is titanium, titanium alloy, nickel, or nickel metal.
[0010] Preferably, in step S1, the metal device is placed in ketone reagent, water and alcohol reagent in sequence for ultrasonic cleaning for 1 to 20 minutes respectively, and the metal substrate A is cleaned with water before each change of cleaning reagent. After cleaning, it is naturally dried at room temperature for 1 to 20 minutes.
[0011] Preferably, the ketone reagent is selected from one or a combination of several of acetone and butanone; the alcohol reagent is selected from one or a combination of several of n-propanol, isopropanol, or ethanol; and the water is deionized water or distilled water.
[0012] Preferably, in step S2, the oxidation reaction of the metal substrate A is carried out in a sealed heating chamber, the set temperature is 80~200℃, the preset heating time is 8~200 minutes, and the oxygen-containing atmosphere is an air atmosphere or an oxygen atmosphere.
[0013] Preferably, in step S2, the sealed heating chamber is a drying oven or a high-temperature tubular furnace.
[0014] Preferably, in step S3, the acid solution is one or a mixture of several of oxalic acid, hydrochloric acid, or sulfuric acid, and the concentration of the acid solution is 0.1~50% w / w.
[0015] Preferably, in step S3, the reaction container holding the acidic solution is heated to an acid etching reaction temperature of 25~100°C using a constant temperature water bath, oil bath, or microwave heating. The metal substrate B is immersed in the predetermined reaction container holding the acidic solution, the reaction container is sealed, and the acid etching process is carried out at a constant temperature for 1~60 minutes to obtain the metal substrate C.
[0016] Preferably, in step S4, the metal substrate C obtained by acid etching in step S3 is ultrasonically cleaned with deionized water and anhydrous ethanol for 1-20 minutes in sequence, and then placed in room temperature air to dry naturally, thereby obtaining a metal substrate device with a nanopillar-modified functional surface.
[0017] The present invention also provides a metal substrate device with a nanopillar-modified functionalized surface, which is prepared by the preparation method of the metal substrate device with nanopillar-modified functionalized surface as described in any of the preceding claims.
[0018] This invention relates to a wet etching process. First, a metal substrate A is obtained by surface cleaning. Then, an oxide layer thickening treatment is performed on the cleaned metal substrate A to ensure uniform oxide layer formation and increased oxide layer thickness on the surface of the metal substrate B. Next, an acidic solution is used as the metal etching agent, and the metal device is immersed in the acidic solution heated in a water bath for etching to obtain a metal substrate C. Finally, after cleaning and drying, a metal substrate device with a nanopillar-modified functionalized surface is obtained. The metal substrate device with a nanopillar-modified functionalized surface and its preparation method provided by this invention have at least the following advantages: The nanopillar array on the surface of the prepared metal substrate device with nanopillar-modified functionalized surface has good dispersion and uniformity, with uniform surface morphology and size and high consistency. The preparation process involved in this invention is simple and energy-efficient, requiring no expensive equipment or complex preparation procedures. The preparation method is simple and efficient, and suitable for large-scale production. The preparation conditions involved in this invention are mild and easy to implement. The solution used in the acid etching process is not only inexpensive but also reusable, giving the entire process a significant economic advantage. The surface structure of the metal substrate devices with nanopillar-modified functionalized surfaces obtained from different batches is consistent, with good reproducibility, making them suitable for mass production. Compared with traditional wet etching and laser ablation, this invention has significant advantages such as high efficiency, speed, low cost and ease of large-scale production, and is expected to be widely used in the field of surface modification of metal devices.
[0019] The metal substrate device with nanopillar-modified functionalized surface prepared in this invention can be used to process metal devices in the field of energy storage and conversion technology, such as bipolar plates (BP), porous transport layers (PTL), nickel alloy plates and other metal electrodes in electrolytic cells, fuel cell electrochemical devices.
[0020] This invention uses an acidic solution of a specific concentration (0.1~50% w / w) for etching to form an ordered array on the surface of a metal device; In this invention, the metal substrate A is kept at a temperature of 80~200°C in an air or oxygen atmosphere for 10~300 minutes, and different oxidation effects are achieved by controlling the temperature and time of oxide layer thickening on the surface of the metal device. This invention achieves the regulation of the microstructure of metal surfaces by controlling the water bath temperature and etching time; This invention employs a multi-step ultrasonic cleaning process in a specific sequence (ketone reagents, deionized water, and alcohol reagents) to ensure thorough cleaning of the device surface. Attached Figure Description
[0021] The accompanying drawings, as part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments and descriptions of the invention are used to explain the invention, but do not constitute an undue limitation of the invention. Obviously, the drawings described below are merely some embodiments, and those skilled in the art can obtain other drawings based on these drawings without creative effort. In the drawings: Figure 1 The image shows a scanning electron microscope image of the metal substrate device with a nanopillar-modified functionalized surface prepared in Example 1.
[0022] Figure 2 This is a scanning electron microscope image of the metal substrate device with a nanopillar-modified functionalized surface prepared in Example 2.
[0023] Figure 3 This is a scanning electron microscope image of the metal substrate device with a nanopillar-modified functionalized surface prepared in Example 3. Detailed Implementation
[0024] The technical problems solved by the embodiments of the present invention, the technical solutions adopted, and the technical effects achieved will be clearly and completely described below with reference to the accompanying drawings and specific embodiments. Obviously, the described embodiments are only a part of the embodiments of this application, and not all of them. Based on the embodiments in this application, all other equivalent or obvious variations of embodiments obtained by those skilled in the art without creative effort fall within the protection scope of the present invention. The embodiments of the present invention can be embodied in various different ways as defined and covered by the claims.
[0025] It should be noted that many specific details are given in the following description for ease of understanding. However, it is obvious that the present invention may be implemented without these specific details.
[0026] It should be noted that, in the absence of explicit limitations or conflicts, the various embodiments and their technical features in this invention can be combined with each other to form a technical solution.
[0027] Example 1: Step S1: The sintered titanium sheet was sequentially ultrasonically cleaned in acetone, deionized water, and anhydrous ethanol for 10 minutes each to remove surface foreign matter. Before each change of cleaning reagent, the metal components were cleaned with deionized water to ensure surface cleanliness. After cleaning, the components were allowed to air dry at room temperature for 10 minutes. The cleaned metal substrate A was obtained.
[0028] Step S2: Place the cleaned metal substrate A from Step S1 inside the drying oven, ensuring an appropriate distance between metal substrate A and the inner walls and partitions so that metal substrate A can be fully exposed to air or oxygen. Before placing metal substrate A, carefully inspect the inside of the drying oven to ensure it is clean and free of any residue, guaranteeing a pure processing environment. Increase the temperature at a rate of 2℃ / min, setting the temperature within the target range of 80℃, and heat for 30 minutes (room temperature 20℃). During heating, maintain an air or oxygen atmosphere inside the drying oven to promote the formation of the oxide layer on the metal surface. After reaching the set temperature, the drying oven enters a constant temperature holding phase for 60 minutes to ensure a uniform and stable thickening of the oxide layer, resulting in a metal substrate B with a thickened oxide layer.
[0029] Step S3: Seal a 10-20% w / w hydrochloric acid solution in a beaker; place the beaker in a constant temperature water bath and heat it to 54°C. Immerse the metal substrate B obtained in step S2 into the preheated acidic solution, seal the beaker, and perform the water bath etching process.
[0030] Step S4: The metal substrate C obtained in step S3 is ultrasonically cleaned with deionized water and anhydrous ethanol for 5 minutes in sequence to remove residual acid and etching products, and then placed in room temperature air to dry naturally to obtain a surface-modified sample, which is the titanium metal substrate device with nanopillar array prepared in this invention.
[0031] Example 2: Step S1: The sintered titanium sheet was sequentially ultrasonically cleaned in acetone, deionized water, and anhydrous ethanol for 10 minutes each to remove surface foreign matter. Before each change of cleaning reagent, the metal components were cleaned with deionized water to ensure surface cleanliness. After cleaning, the components were allowed to air dry at room temperature for 10 minutes. The cleaned metal substrate A was obtained.
[0032] Step S2: Place the cleaned metal substrate A from Step S1 inside the drying oven, ensuring an appropriate distance between the metal substrate A and the inner walls and partitions so that the metal substrate A can be fully exposed to air or oxygen. Before placing the metal substrate A, carefully inspect the inside of the drying oven to ensure it is clean and free of any residue, guaranteeing a pure processing environment. Increase the temperature at a rate of 2℃ / min, setting the temperature within the target range of 120℃, and heat for 50 minutes (room temperature 20℃). During heating, maintain an air or oxygen atmosphere inside the drying oven to promote the formation of the oxide layer on the metal surface. After reaching the set temperature, the drying oven enters a constant temperature holding phase for 90 minutes to ensure a uniform and stable thickening of the oxide layer, resulting in a metal substrate B with a thickened oxide layer.
[0033] Step S3: Seal a 20-30% w / w hydrochloric acid solution in a beaker; place the beaker in a constant temperature water bath and heat it to 57°C. Immerse the metal substrate B obtained in step S2 into the preheated acidic solution, seal the beaker, and perform the water bath etching process.
[0034] Step S4: The metal substrate C obtained in step S3 is ultrasonically cleaned with deionized water and anhydrous ethanol for 10 minutes in sequence to remove residual acid and etching products, and then placed in room temperature air to dry naturally to obtain a surface-modified sample, which is the metal substrate device with nanopillar modified functional surface of the present invention.
[0035] Example 3: Step S1: The sintered titanium sheet was sequentially ultrasonically cleaned in acetone, deionized water, and anhydrous ethanol for 10 minutes each to remove surface foreign matter. Before each change of cleaning reagent, the metal components were cleaned with deionized water to ensure surface cleanliness. After cleaning, the components were allowed to air dry at room temperature for 10 minutes. The cleaned metal substrate A was obtained.
[0036] Step S2: Place the cleaned metal substrate A from Step S1 inside the drying oven, ensuring an appropriate distance between the metal substrate A and the inner walls and partitions so that the metal substrate A can be fully exposed to air or oxygen. Before placing the metal substrate A, carefully inspect the inside of the drying oven to ensure it is clean and free of any residue, guaranteeing a pure processing environment. Increase the temperature at a rate of 2℃ / min, setting the temperature within the target range of 160℃, and heat for 70 minutes (room temperature 20℃). During heating, maintain an air or oxygen atmosphere inside the drying oven to promote the formation of the oxide layer on the metal surface. After reaching the set temperature, the drying oven enters a constant temperature holding phase for 120 minutes to ensure a uniform and stable thickening of the oxide layer, resulting in a metal substrate B with a thickened oxide layer.
[0037] Step S3: Seal a 30-40% w / w hydrochloric acid solution in a beaker; place the beaker in a constant temperature water bath and heat it to 60°C. Immerse the metal substrate B obtained in step S2 into the preheated acidic solution, seal the beaker, and perform the water bath etching process.
[0038] Step S4: The metal substrate C obtained in step S3 is ultrasonically cleaned with deionized water and anhydrous ethanol for 20 minutes in sequence to remove residual acid and etching products, and then placed in room temperature air to dry naturally to obtain a surface-modified sample, which is the metal substrate device with nanopillar modified functional surface of the present invention.
[0039] Please combine them together Figure 1-3 As can be seen, the metal substrate devices with nanopillar-modified functional surfaces prepared in Examples 1-3 of the present invention have uniform surface morphology and size after acid etching, exhibiting high consistency; the height of the nanopillar array can be adjusted according to the thickness of the oxide layer.
[0040] The scope of protection of this invention is not limited to the process parameters and conditions listed in the specific embodiments above. Any reasonable adjustments or modifications to the specific parameters and conditions in the above process steps based on the preparation process and ideas involved in this invention, while still adhering to the same technical principles and objectives, are all within the scope of protection of this invention. For example, appropriate adjustments to the specific type of cleaning solvent (replacing it with other solvents with similar cleaning effects within a reasonable range), the type of acid used for acid etching (replacing it with other acids capable of achieving similar etching effects within a reasonable range), and the specific operational details of each step, as long as these adjusted technical solutions still fall within the technical concept scope of this invention, should be protected by this invention.
[0041] The above-described embodiments are only used to illustrate the technical solutions of the present invention, and are not intended to limit it. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some of the technical features. Such modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the spirit and scope of the technical solutions of the embodiments of the present invention, and should all be included within the protection scope of the present invention.
Claims
1. A method for fabricating a metal substrate device with a nanopillar-modified functionalized surface, characterized in that, Including the following steps: S1 provides a cleaned metal substrate A; S2, in an oxygen-containing atmosphere, the metal substrate A is heated to a set temperature at a heating rate of 1~10℃ / min within a preset heating time, and held at that temperature for 10~300 minutes to obtain a metal substrate B with a thickened oxide layer. S3, the metal substrate B is acid-etched in an acidic solution of 0.1% to 50% w / w at a temperature of 25 to 100°C to obtain the metal substrate C; S4. The metal substrate C obtained by acid etching in step S3 is cleaned with anhydrous ethanol and dried to obtain a metal substrate device with a nanopillar-modified functional surface.
2. The method for fabricating a metal substrate device with a nanopillar-modified functionalized surface according to claim 1, characterized in that, In step S1, the thickness of the metal substrate A is 100nm~10mm, and the material of the metal substrate A is titanium, titanium alloy, nickel, or nickel alloy.
3. The method for fabricating a metal substrate device with a nanopillar-modified functionalized surface according to claim 2, characterized in that, In step S1, the metal device is placed in ketone reagent, deionized water and alcohol reagent in sequence for ultrasonic cleaning for 1 to 20 minutes. Before each change of cleaning reagent, the metal substrate A is cleaned with deionized water. After cleaning, it is naturally dried at room temperature for 1 to 20 minutes.
4. The method for fabricating a metal substrate device with a nanopillar-modified functionalized surface according to claim 3, characterized in that, The ketone reagent is selected from one or a combination of acetone and butanone; the alcohol reagent is selected from one or a combination of n-propanol, isopropanol or ethanol; and the water is deionized water or distilled water.
5. The method for fabricating a metal substrate device with a nanopillar-modified functionalized surface according to claim 1, characterized in that, In step S2, the oxidation reaction of the metal substrate A is carried out in a sealed heating chamber, the set temperature is 80~200℃, the preset heating time is 8~200 minutes, and the oxygen-containing atmosphere is an air atmosphere or an oxygen atmosphere.
6. The method for fabricating a metal substrate device with a nanopillar-modified functionalized surface according to claim 5, characterized in that, In step S2, the sealed heating chamber is a drying oven or a high-temperature tubular furnace.
7. The method for fabricating a metal substrate device with a nanopillar-modified functionalized surface according to claim 1, characterized in that, In step S3, the acid solution is one or a combination of oxalic acid, hydrochloric acid, or sulfuric acid, and the concentration of the acid solution is 0.1~50% w / w.
8. The method for fabricating a metal substrate device with a nanopillar-modified functionalized surface according to claim 7, characterized in that, In step S3, the reaction container holding the acidic solution is heated to the acid etching reaction temperature of 25~100℃ by constant temperature water bath, oil bath or microwave heating. The metal substrate B is immersed in the preset reaction container holding the acidic solution, the reaction container is sealed, and the acid etching process is carried out at a constant temperature at the acid etching reaction temperature for 1~60 minutes to obtain the metal substrate C.
9. The method for fabricating a metal substrate device with a nanopillar-modified functionalized surface according to claim 1, characterized in that, In step S4, the metal substrate C obtained by acid etching in step S3 is ultrasonically cleaned with deionized water and anhydrous ethanol for 1-20 minutes in sequence, and then placed in room temperature air to dry naturally, so as to obtain a metal substrate device with a nanopillar-modified functional surface.
10. A metal substrate device with a nanopillar-modified functionalized surface, characterized in that, The device is prepared using the method described in any one of claims 1-9 for fabricating a metal substrate device with a nanopillar-modified functionalized surface.