Etching-deposition coupling steel super-hydrophobic surface, preparation method and application
By constructing a three-layer structure on the steel surface using an etching-deposition coupling method, the problem of easy damage to the steel surface modified by chemical deposition method is solved, and the superhydrophobic properties and corrosion resistance are improved, making it suitable for anti-icing and anti-corrosion in low temperature and high humidity environments.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- ANGANG STEEL CO LTD
- Filing Date
- 2026-01-12
- Publication Date
- 2026-04-21
AI Technical Summary
The superhydrophobic properties of steel surfaces modified by existing chemical deposition methods are easily damaged, resulting in only a small improvement in corrosion resistance and failing to effectively solve the problems of icing and corrosion in low-temperature and high-humidity environments.
A three-layer structure is constructed on the steel surface using an etching-deposition coupling method: a chemical etching layer, a chemical deposition layer, and a low surface energy modification layer. These layers are connected by molecular/atomic forces to form a multi-level rough structure and a dissimilar metal layer. Combined with the low surface energy modification layer, the superhydrophobic properties are improved.
It significantly improves the superhydrophobicity and corrosion resistance of steel surfaces, and its corrosion electrochemical parameters are superior to those of the single chemical deposition method, making it suitable for anti-icing and anti-corrosion in low-temperature and high-humidity environments.
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Figure CN121896641A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of chemical plating and material surface modification technology, specifically involving an etching-deposition coupled steel superhydrophobic surface, its preparation method and application. Background Technology
[0002] Low-alloy steel materials are widely used in the construction of ships, offshore platforms, bridges and other industries. Traditional low-alloy steel materials will encounter problems such as water condensation and icing and surface corrosion when exposed to humid environments during service. In particular, steel structures serving in extremely cold regions are prone to surface icing due to the characteristics of low temperature and high humidity service environment, which threatens service safety. At the same time, water and ice will also cause corrosion to steel materials.
[0003] In recent years, superhydrophobic materials have attracted widespread attention due to their unique superhydrophobic properties. Surfaces with a static contact angle with water greater than 150° are generally defined as superhydrophobic surfaces, which have application value in many areas such as self-cleaning, anti-fouling, anti-corrosion, and anti-icing. A micro / nano-layered structure and low surface energy are prerequisites for achieving superhydrophobic properties. Currently, superhydrophobic modification of steel surfaces is generally achieved by changing their surface roughness or by modifying them with low surface energy materials. Methods for superhydrophobic surface modification mainly include deposition methods, sol-gel methods, hydrothermal synthesis methods, chemical etching methods, template methods, and laser etching methods. Typically, a micro / nano-structure is first prepared on the surface, and then a superhydrophobic surface is obtained through modification with low surface energy materials. Among these methods, vapor deposition and laser etching require more sophisticated equipment, are expensive, and have low production efficiency, making them unsuitable for large-scale production. Hydrothermal synthesis involves reactions in a sealed high-pressure autoclave, resulting in high energy consumption. Template methods use soft or hard mold replication technology, which is unsuitable for products with complex shapes and has certain limitations. Chemical etching uses acidic or alkaline etching solutions for surface etching, achieving multiple microstructures with lower production costs and simpler processes and equipment, but it results in material loss. Chemical deposition can deposit other metallic elements on the surface of steel materials to protect the base metal, but the deposited layer has weak adhesion and is easily removed, losing its superhydrophobic properties.
[0004] Currently, superhydrophobic surfaces constructed through chemical deposition modification of steel surfaces suffer from the problem of easy surface damage leading to the loss of superhydrophobic properties, resulting in only a limited improvement in corrosion resistance compared to the steel substrate. Developing an etching-deposition coupled superhydrophobic steel surface and its preparation method can integrate the advantages of both chemical etching and chemical deposition methods, further enhancing the corrosion resistance of superhydrophobic surfaces. Summary of the Invention
[0005] To address the problem of superhydrophobic modification of steel material surfaces, this invention provides an etching-deposition coupled superhydrophobic steel surface and its preparation method, overcoming the shortcomings of existing technologies. More specifically, it is a method for constructing a superhydrophobic surface on a steel surface and achieving superhydrophobic modification of the steel surface through the principle of chemical etching-chemical deposition.
[0006] According to a first aspect of the present invention, an etching-deposition coupled steel superhydrophobic surface is provided, the surface having a three-layer structure, including a chemical etching layer, a chemical deposition layer and a low surface energy modification layer, wherein the synthetic etching layer is a multi-level rough structure produced by chemical etching, the chemical deposition layer is a dissimilar metal layer produced by chemical deposition, and the low surface energy modification layer is a low surface energy organic monolayer.
[0007] Based on the above technical solution, the thickness of the chemical etching layer is 10~50μm, which has the function of increasing surface roughness.
[0008] Based on the above technical solution, the thickness of the chemically deposited layer is 1~50μm, which has the function of further increasing the surface roughness and protecting the base metal.
[0009] Based on the above technical solution, the thickness of the low surface energy modification layer is 2~5nm, which has the function of increasing the superhydrophobic properties of the surface.
[0010] Based on the above technical solution, the interlayers of the etching-deposition coupled steel superhydrophobic surface are connected by molecular / atomic forces, wherein the chemical etching layer is directly connected to the steel substrate, the chemical deposition layer is bonded to the chemical etching layer through interatomic forces, and the low surface energy modification layer is bonded to the chemical deposition layer through coordination bonds.
[0011] Based on the above technical solution, the substrate of the etching-deposition coupled steel superhydrophobic surface is selected from shipbuilding steel and marine engineering steel.
[0012] Based on the above technical solution, the substrate of the etching-deposition coupled steel superhydrophobic surface is selected from at least one of A, AH32, AH36, EH36, FH36 and VL4-4.
[0013] Based on the above technical solution, the solution used to prepare the chemical etching layer is an etching solution; The etching solution is an acidic inorganic solution composed of inorganic acid, inorganic salt and water; The inorganic acid is selected from at least one of hydrochloric acid, nitric acid, and hydrofluoric acid; The inorganic salt is selected from at least one of ferric chloride, ferric sulfate, and ferric nitrate; The etching solution contains 5-25 wt% acid, 5-25 wt% inorganic salt, and the remainder is water.
[0014] Based on the above technical solution, the solution for preparing the chemical deposition layer is a deposition solution; The sediment consists of a metal salt that is less reactive than iron and water. The metal salt is selected from at least one of copper chloride, copper sulfate, and nickel sulfate; The concentration of the metallic orthosalt in the sediment is 0.01 ~ 0.1 mol / L.
[0015] Based on the above technical solution, the solution for preparing the low surface energy modified layer is the modification liquid; The modification solution is composed of organic low surface energy substances and organic solvents; The organic low surface energy substance is selected from at least one of stearic acid, myristic acid, and palmitic acid; The organic solvent is selected from at least one of ethanol, n-propanol, isopropanol, and acetone; The concentration of the organic low surface energy substance in the modified solution is 0.01~0.1 mol / L.
[0016] According to a second aspect of the present invention, a method for preparing an etching-deposition coupled superhydrophobic steel surface is provided, characterized by comprising the following steps: steel surface pretreatment - chemical etching - chemical deposition - low surface energy modification - cleaning - drying; Steel surface pretreatment: Grind with sandpaper to 240~1200#, remove oil, degrease, and clean with deionized water to obtain the steel sample after surface pretreatment; Chemical etching: The pre-treated steel sample is placed in an etching solution for chemical etching. After etching, the steel sample is removed and cleaned with deionized water to obtain the chemically etched steel sample. Chemical deposition: The chemically etched steel sample is placed in a deposition solution for chemical deposition. After deposition, the steel sample is removed and washed sequentially with deionized water and anhydrous ethanol to obtain the chemically deposited steel sample. Low surface energy modification: The steel sample after chemical deposition is placed in a modification solution for low surface energy modification to obtain a steel sample with low surface energy modification.
[0017] Based on the above technical solution, the chemical etching time is 10~120 min; The chemical deposition time is 0.5~10 min; The time for the low surface energy modification is 30~120 min.
[0018] Based on the above technical solution, the etching solution in the chemical etching is an acidic inorganic solution, one of hydrochloric acid-ferric chloride solution, nitric acid-ferric nitrate solution, hydrofluoric acid-ferric sulfate solution, and hydrochloric acid-ferric sulfate solution, wherein the mass fraction of acid is 5~25wt%, the mass fraction of inorganic salt is 5~25wt%, and the remainder is water; The deposition solution for the chemical deposition is a copper chloride solution, a copper sulfate solution, or a nickel sulfate solution, with a concentration of 0.01 ~ 0.1 mol / L; The low surface energy modification solution is at least one of stearic acid ethanol solution, stearic acid isopropanol solution, myristic acid isopropanol-acetone solution, and palmitic acid n-propanol solution, wherein the concentration of the low surface energy substance is 0.01~0.1 mol / L.
[0019] Based on the above technical solution, the cleaning process specifically involves: placing the low surface energy modified steel sample in ethanol for cleaning to obtain the cleaned steel sample; The drying process specifically involves drying the cleaned steel sample at 10~80℃ for 1~10 minutes to obtain a steel plate with a superhydrophobic surface.
[0020] According to a third aspect of the invention, an application of an etch-deposition coupled steel superhydrophobic surface is provided in a corrosion-resistant environment.
[0021] Beneficial effects The technical solution disclosed in this invention prepares steel with a superhydrophobic surface through an etching-deposition coupling method. The surface has a three-layer structure, including a chemical etching layer, a chemical deposition layer, and a low surface energy modification layer. The chemical etching layer is a multi-level rough structure produced by chemical etching, the chemical deposition layer is a dissimilar metal layer produced by chemical deposition, and the low surface energy modification layer is a low surface energy organic monolayer. This method can endow ordinary steel materials with superhydrophobic properties. Compared with the superhydrophobic surface of steel with single chemical deposition, the corrosion resistance of the superhydrophobic surface of steel with etching-deposition coupling is further improved, and its corrosion electrochemical parameters are better. Attached Figure Description
[0022] Figure 1 These are schematic diagrams of the etching-deposition coupled steel superhydrophobic surface structure described in Embodiments 1-3 of the present invention; Figure 2 The AC impedance spectrum of the superhydrophobic surface of the ship plate steel A plate in Embodiment 1 and Comparative Example 1 of the present invention; Figure 3 The linear polarization curves of the superhydrophobic surface of the ship plate A in Embodiment 1 and Comparative Example 1 of the present invention are shown. Figure 4 The AC impedance spectrum of the superhydrophobic surface of ship plate steel FH36 in Embodiment 2 and Comparative Example 2 of the present invention; Figure 5 The linear polarization curves of the superhydrophobic surface of ship plate steel FH36 in Embodiment 2 and Comparative Example 2 of the present invention are shown. Figure 6 The AC impedance spectrum of the superhydrophobic surface of marine steel VL4-4 in Embodiment 3 and Comparative Example 3 of the present invention; Figure 7The linear polarization curves of the superhydrophobic surface of marine steel VL4-4 in Embodiment 3 and Comparative Example 3 of the present invention are shown. Detailed Implementation
[0023] To make the objectives and technical solutions of this invention clearer, the following embodiments are provided for further explanation. However, the scope of protection of this invention is not limited to these embodiments; the embodiments are merely for illustrative purposes. Those skilled in the art should understand that any changes or equivalent substitutions that do not depart from the concept of this invention are included within the scope of protection of this invention.
[0024] Unless otherwise specified, all reagents and raw materials used in this invention are obtained through purchase.
[0025] Example 1 The surface of the ship plate steel A was sanded with wet sandpaper to 1200#, and then degreased, degreased, and cleaned with deionized water. The pretreated steel sample was chemically etched using a 25wt% hydrochloric acid + 5wt% ferric chloride aqueous solution for 10 minutes, followed by cleaning with deionized water. A 0.05mol / L copper sulfate solution was used for chemical deposition on the etched steel sample for 5 minutes, followed by cleaning with deionized water and anhydrous ethanol. The chemically deposited steel surface was modified with a 0.05mol / L stearic acid-ethanol solution for 120 minutes. The modified steel sample was then cleaned with anhydrous ethanol and dried at 20℃ for 10 minutes, resulting in a superhydrophobic surface of the ship plate steel A (chemically etched layer thickness 10μm, chemically deposited layer thickness 30μm, low surface energy modification layer thickness 5nm). A schematic diagram of the superhydrophobic surface structure is shown below. Figure 1 .
[0026] The superhydrophobic surface of the etched-deposition coupled steel plate A was placed in a 3.5wt% sodium chloride solution to test its corrosion resistance. The test results are shown in [Figure number missing]. Figure 2 , 3 It can be seen that in a 3.5wt% sodium chloride solution, its impedance arc radius and polarization resistance are more than twice that of the superhydrophobic surface of the A-plate of ship plate steel by chemical deposition.
[0027] Example 2 The surface of FH36 ship plate steel was sanded with water sandpaper to 600#, and then degreased, degreased, and cleaned with deionized water. The pretreated steel sample was chemically etched using a 10wt% hydrochloric acid + 25wt% ferric chloride aqueous solution for 60 min, followed by cleaning with deionized water. A 0.1mol / L copper chloride solution was used as the chemical deposition solution to chemically deposit onto the etched steel sample for 0.5 min, followed by cleaning with deionized water and anhydrous ethanol. The chemically deposited steel surface was modified with a 0.01mol / L isopropanol-acetone solution for 30 min. The modified steel sample was then cleaned with ethanol and dried at 80℃ for 1 min, resulting in a superhydrophobic surface of FH36 ship plate steel with etch-deposition coupling (chemical etching layer thickness 20 μm, chemical deposition layer thickness 1 μm, and low surface energy modification layer thickness 2 nm). A schematic diagram of the superhydrophobic surface structure is shown below. Figure 1 .
[0028] The superhydrophobic surface of the fabricated FH36 etch-deposition coupled steel was placed in a 3.5wt% sodium chloride solution to test its corrosion resistance. The test results are shown below. Figure 4 , 5 It can be seen that in a 3.5wt% sodium chloride solution, its impedance arc radius and polarization resistance are more than twice that of the superhydrophobic surface of FH36 steel plate steel obtained by chemical deposition.
[0029] Example 3 The surface of the marine engineering steel VL4-4 was polished to 1000# with wet sandpaper, and then degreased, degreased, and cleaned with deionized water. The pretreated steel sample was chemically etched using a 5wt% nitric acid + 5wt% ferric nitrate aqueous solution for 120 min, followed by cleaning with deionized water. Chemical deposition was performed on the chemically etched steel sample using a 0.01 mol / L nickel sulfate solution for 10 min, followed by cleaning with deionized water and anhydrous ethanol. The chemically deposited steel surface was modified with a 0.1 mol / L palmitic acid-propanol solution for 60 min. The modified steel sample was then cleaned with ethanol and dried at 50℃ for 5 min, resulting in a VL4-4 etch-deposition coupled steel superhydrophobic surface (chemically etched layer thickness 50 μm, chemically deposited layer thickness 50 μm, low surface energy modification layer thickness 3 nm). A schematic diagram of the superhydrophobic surface structure is shown below. Figure 1 .
[0030] The prepared VL4-4 etch-deposition coupled steel superhydrophobic surface was placed in a 3.5wt% sodium chloride solution to test its corrosion resistance. The test results are shown in [Figure number missing]. Figure 6 , 7It can be seen that in a 3.5wt% sodium chloride solution, its impedance arc radius and polarization resistance are more than twice that of the superhydrophobic surface of marine engineering steel VL4-4 chemically deposited steel.
[0031] Comparative Example 1 Preparation method of superhydrophobic steel surface of ship plate A by chemical deposition: The surface of ship plate A was sanded with water sandpaper to 1200#, and then degreased, degreased, and cleaned with deionized water. Chemical deposition was performed on the pretreated steel sample using 0.05 mol / L copper sulfate solution for 5 min, followed by cleaning with deionized water and anhydrous ethanol. The chemically deposited steel surface was modified with 0.05 mol / L stearic acid ethanol solution for 120 min. The modified steel sample was then cleaned with anhydrous ethanol and dried at 20℃ for 10 min to obtain the superhydrophobic steel surface of ship plate A by chemical deposition. The corrosion resistance of the superhydrophobic steel surface prepared by chemical deposition was tested by placing it in a 3.5 wt% sodium chloride solution. The test results are shown in [Figure number missing]. Figure 2 , 3 .
[0032] Comparative Example 2 Preparation method of superhydrophobic surface of FH36 ship plate steel by chemical deposition: The surface of FH36 ship plate steel was sanded with water sandpaper to 600#, and then degreased, degreased, and cleaned with deionized water. A 0.1 mol / L copper chloride solution was used as the chemical deposition solution to chemically deposit the pretreated steel sample for 0.5 min. After deposition, the sample was cleaned sequentially with deionized water and anhydrous ethanol. The chemically deposited steel surface was modified with a 0.01 mol / L isopropanol-acetone solution for 30 min. The modified steel sample was cleaned with ethanol and dried at 80℃ for 1 min to obtain the superhydrophobic surface of FH36 ship plate steel prepared by chemical deposition. The superhydrophobic surface prepared by chemical deposition was placed in a 3.5 wt% sodium chloride solution to test its corrosion resistance. The test results are shown in [Figure number missing]. Figure 4 , 5 .
[0033] Comparative Example 3 Preparation method of superhydrophobic surface of marine engineering steel VL4-4 by chemical deposition: The surface of marine engineering steel VL4-4 was sanded with water sandpaper to 1000#, and then degreased, degreased, and cleaned with deionized water. Chemical deposition was performed on the pretreated steel sample using 0.01 mol / L nickel sulfate solution for 10 min, followed by cleaning with deionized water and anhydrous ethanol. The chemically deposited steel surface was modified with 0.1 mol / L palmitic acid-propanol solution for 60 min. The modified steel sample was then cleaned with ethanol and dried at 50℃ for 5 min to obtain the superhydrophobic surface of marine engineering steel VL4-4 prepared by chemical deposition. The superhydrophobic surface prepared by chemical deposition was placed in a 3.5 wt% sodium chloride solution to test its corrosion resistance. The test results are shown in [Figure number missing]. Figure 6 , 7 .
[0034] The above description is merely a few embodiments of this application and is not intended to limit this application in any way. Although this application discloses preferred embodiments as described above, it is not intended to limit this application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of this application using the disclosed technical content are equivalent to equivalent implementation cases and fall within the scope of the technical solution.
Claims
1. An etching-deposition coupled superhydrophobic steel surface, characterized in that, The surface has a three-layer structure, including a chemical etching layer, a chemical deposition layer, and a low surface energy modification layer. The chemical etching layer is a multi-level rough structure produced by chemical etching and is directly connected to the steel substrate. The chemical deposition layer is a dissimilar metal layer produced by chemical deposition and is bonded to the chemical etching layer through interatomic forces. The low surface energy modification layer is a low surface energy organic monolayer and is bonded to the chemical deposition layer through coordination bonds. The thickness of the chemically etched layer is 10~50μm; The thickness of the chemically deposited layer is 1~50μm; The thickness of the low surface energy modification layer is 2~5 nm.
2. The etching-deposition coupled superhydrophobic steel surface according to claim 1, characterized in that, The solution used to prepare the chemically etched layer is called an etching solution; The etching solution is an acidic inorganic solution composed of inorganic acid, inorganic salt and water; The inorganic acid is selected from at least one of hydrochloric acid, nitric acid, and hydrofluoric acid; The inorganic salt is selected from at least one of ferric chloride, ferric sulfate, and ferric nitrate; The etching solution contains 5-25 wt% acid, 5-25 wt% inorganic salt, and the remainder is water.
3. The etching-deposition coupled superhydrophobic steel surface according to claim 1, characterized in that, The solution used to prepare the chemical deposition layer is called the deposition solution; The sediment consists of a metal salt that is less reactive than iron and water. The metal salt is selected from at least one of copper chloride, copper sulfate, and nickel sulfate; The concentration of the metallic orthosalt in the sediment is 0.01~0.1 mol / L.
4. The etching-deposition coupled superhydrophobic steel surface according to claim 1, characterized in that, The solution used to prepare the low surface energy modified layer is the modification solution; The modification solution is composed of organic low surface energy substances and organic solvents; The organic low surface energy substance is selected from at least one of stearic acid, myristic acid, and palmitic acid; The organic solvent is selected from at least one of ethanol, n-propanol, isopropanol, and acetone; The concentration of the organic low surface energy substance in the modified solution is 0.01~0.1 mol / L.
5. The method for preparing the etching-deposition coupled superhydrophobic steel surface according to any one of claims 1 to 4, characterized in that, The process includes the following steps: steel surface pretreatment - chemical etching - chemical deposition - low surface energy modification - cleaning - drying; Steel surface pretreatment: Grind with sandpaper to 240~1200#, remove oil, degrease, and clean with deionized water to obtain the steel sample after surface pretreatment; Chemical etching: The pre-treated steel sample is placed in an etching solution for chemical etching. After etching, the steel sample is removed and cleaned with deionized water to obtain the chemically etched steel sample. Chemical deposition: The chemically etched steel sample is placed in a deposition solution for chemical deposition. After deposition, the steel sample is removed and washed sequentially with deionized water and anhydrous ethanol to obtain the chemically deposited steel sample. Low surface energy modification: The steel sample after chemical deposition is placed in a modification solution for low surface energy modification to obtain a steel sample with low surface energy modification.
6. The preparation method according to claim 5, characterized in that, The chemical etching time is 10~120 min; The chemical deposition time is 0.5~10 min; The low surface energy modification time is 30~120 min.
7. The preparation method according to claim 5, characterized in that, The etching solution used in the chemical etching is an acidic inorganic solution, preferably one of hydrochloric acid-ferric chloride solution, nitric acid-ferric nitrate solution, hydrofluoric acid-ferric sulfate solution, or hydrochloric acid-ferric sulfate solution, wherein the mass fraction of acid is 5-25 wt%, the mass fraction of inorganic salt is 5-25 wt%, and the remainder is water; The deposition solution for the chemical deposition is a copper chloride solution, a copper sulfate solution, or a nickel sulfate solution, with a concentration of 0.01~0.1 mol / L; The low surface energy modification solution is at least one of stearic acid ethanol solution, stearic acid isopropanol solution, myristic acid isopropanol-acetone solution, and palmitic acid n-propanol solution, wherein the concentration of the low surface energy substance is 0.01~0.1 mol / L.
8. The preparation method according to claim 5, characterized in that, The cleaning process specifically involves placing the low surface energy modified steel sample in ethanol for cleaning to obtain a cleaned steel sample. The drying process specifically involves drying the cleaned steel sample at 10~80℃ for 1~10 minutes to obtain a steel plate with a superhydrophobic surface.
9. The application of the etch-deposition coupled steel superhydrophobic surface prepared by any one of the preparation methods of claims 5 to 8 in a corrosion-resistant environment.
10. The etching-deposition coupled superhydrophobic steel surface according to claim 1, characterized in that, The substrate of the etching-deposition coupled steel superhydrophobic surface is selected from one of shipbuilding steel and marine engineering steel; Preferably, the substrate of the etch-deposition coupled steel superhydrophobic surface is selected from at least one of A, AH32, AH36, EH36, FH36 and VL4-4.