A method for preparing a steel superhydrophobic anti-icing surface based on chemical deposition

Abstract

The present invention relates to a preparation method of a super-hydrophobic and anti-icing surface of steel based on chemical deposition, wherein a rough structure is constructed on the steel surface by chemical deposition, and then the super-hydrophobic and anti-icing surface of steel is obtained by low surface energy modification, specifically comprising: 1) chemical deposition: placing a steel sample in a chemical deposition solution for chemical deposition, wherein the deposition solution is composed of salt and water, wherein the salt component is a positive salt of copper, the salt concentration is 0.001-0.1 mol / L, and the deposition time is 10-500s; 2) low surface energy modification: modifying the steel surface after chemical deposition with a modifier, wherein the modifier is composed of a low surface energy substance and an organic solvent, the concentration of the low surface energy substance in the modifier is 0.01-0.1 mol / L, and the modification time is 10-120 min. The preparation method can realize the super-hydrophobic modification of the steel surface, and the obtained steel surface has good super-hydrophobic and anti-icing properties, and the preparation method is simple, safe, easy to implement, and has high application feasibility, and can be applied to the surface protection field of low-alloy steel materials.

Description

Technical Field

[0001] The present invention belongs to the technical field of chemical plating and material surface modification, and in particular relates to a method for preparing a steel super-hydrophobic anti-icing surface based on chemical deposition, specifically a method for constructing a rough structure on the steel surface by chemical deposition, and then obtaining the steel super-hydrophobic anti-icing surface by low surface energy modification. Background Art

[0002] Low-alloy steel materials are widely used in the construction of ships, offshore platforms, bridges and other industries. Traditional low-alloy steel materials may encounter problems such as water icing and surface corrosion when exposed to humid environments during service. Especially for steel structures serving in extremely cold areas, due to the low temperature and high humidity service environment, it is very easy to form ice on the surface, threatening service safety. At the same time, water and ice will also cause corrosion to steel materials.

[0003] In recent years, super-hydrophobic materials have attracted widespread attention due to their unique super-hydrophobic properties on the surface. The surface with a static contact angle of more than 150° with water is usually defined as a super-hydrophobic surface, which has application value in many aspects such as self-cleaning, anti-pollution, anti-corrosion, and anti-icing. Having a micro-nano hierarchical structure and lower surface energy is a prerequisite for achieving super-hydrophobic properties. At present, the super-hydrophobic modification of steel surfaces can generally be achieved by changing its surface roughness or modifying with low surface energy substances. The method for super-hydrophobic surface modification mainly includes methods such as deposition method, sol-gel method, chemical vapor deposition method, hydrothermal synthesis method, chemical etching method, template method, and laser etching method. Usually, surface micro-nano structure is prepared first, and then super-hydrophobic surface is obtained by modifying with low surface energy substances. Among them, the equipment used in vapor deposition and laser etching is more sophisticated, the equipment is expensive and the production efficiency is low, and it is not suitable for large-scale production; the hydrothermal synthesis method is to react in a sealed autoclave, and the production energy consumption is high; the template method uses soft mold or hard mold replication technology, which is not suitable for products with complex shapes and has certain limitations; the chemical etching method uses acidic or alkaline etching liquid for surface etching treatment, with low production costs, simple processes and equipment, but it will cause material loss and belongs to subtractive manufacturing. The chemical deposition method can deposit other metal elements on the surface of steel materials, which belongs to additive manufacturing and can avoid material loss and waste.

[0004] At present, superhydrophobic steel surfaces are mainly concentrated in the fields of stainless steel and structural steel, and there are few studies on superhydrophobic and anti-icing surfaces of low-alloy steel. Using a simple and economical method to modify the superhydrophobic surface of low-alloy steel is beneficial to improve the surface hydrophobic properties of steel, give the steel surface anti-icing properties, and achieve the purpose of waterproofing, anti-icing and anti-corrosion. Summary of the invention

[0005] The present invention provides a method for preparing a super-hydrophobic and anti-icing surface of steel based on chemical deposition. The preparation method can realize super-hydrophobic modification of the surface of steel. The prepared steel surface has good super-hydrophobic and anti-icing properties. The preparation method is simple, safe, easy to realize, and has high application feasibility. It can be applied to the field of surface protection of low-alloy steel materials.

[0006] In order to achieve the above object, the present invention adopts the following technical solutions:

[0007] A method for preparing a super-hydrophobic and anti-icing steel surface based on chemical deposition, wherein a rough structure is constructed on the steel surface by chemical deposition, and then the super-hydrophobic and anti-icing steel surface is obtained by low surface energy modification. The preparation process is: surface pretreatment → chemical deposition → low surface energy modification → cleaning and drying, specifically including:

[0008] 1) Chemical deposition: The steel sample is placed in a chemical deposition solution for chemical deposition, wherein the deposition solution is composed of salt and water, wherein the salt component is a copper salt, the salt concentration is 0.001 to 0.1 mol / L, and the deposition time is 10 to 500 s;

[0009] 2) Low surface energy modification: The steel surface after chemical deposition is modified by a modifier, wherein the modifier is composed of a low surface energy substance and an organic solvent, the concentration of the low surface energy substance in the modifier is 0.01 to 0.1 mol / L, and the modification time is 10 to 120 min.

[0010] The copper salt is copper chloride or copper sulfate, which is washed with deionized water, ultrasonically cleaned, and then with ethanol after deposition.

[0011] The low surface energy substance includes at least one of fatty acid substances, oxygen silane substances, fluorosilane substances, and thiol substances, and the solvent is at least one of ethanol and acetone.

[0012] The fatty acid substances include stearic acid, myristic acid, perfluorooctanoic acid, and palmitic acid; the oxygen silane substances include methyltrimethoxysilane, vinyltrimethoxysilane, and hexadecyltrimethoxysilane; the fluorosilane substances include perfluorodecyltrimethoxysilane and perfluorooctyltrichlorosilane; and the thiol substances include dodecyl mercaptan and perfluorodecyl mercaptan.

[0013] The surface pretreatment method includes: degreasing, degreasing, and cleaning the steel sample surface with deionized water, and polishing the surface with water sandpaper to 200-1200 mesh.

[0014] The cleaning and drying method comprises: cleaning the modified steel sample with ethanol and drying it at a drying temperature of 20 to 80°C.

[0015] A steel super-hydrophobic anti-icing surface based on chemical deposition comprises a steel substrate, a heterogeneous metal deposition layer and a low surface energy material layer, has a three-layer surface structure, and a static contact angle between the surface and water is greater than 150°.

[0016] The steel substrate is low alloy steel, including but not limited to shipbuilding steel, bridge steel and marine engineering steel; the dissimilar metal deposition layer is a copper deposition layer; the low surface energy substance includes at least one of fatty acid substances, oxysilane substances, fluorosilane substances and thiol substances.

[0017] Under the same service environment, the steel superhydrophobic anti-icing surface reduces surface ice coverage by more than 75% compared to the steel substrate.

[0018] The super-hydrophobic anti-icing surface of steel has anti-icing performance, and its surface ice reduction is more than 75%. That is, in the surface ice test under the same service environment, compared with the steel substrate, the super-hydrophobic anti-icing surface of steel can reduce the surface ice by more than 75%. The surface ice test is carried out in an environmental test chamber with adjustable temperature and humidity. The set temperature is -20℃. After 5mL of deionized water is evenly sprayed on the surface of the sample, it is frozen for 2h, and then the weight gain of the sample is measured. The weight gain of the ice layer per unit area is calculated according to formula (1), and the reduction of surface ice is calculated according to formula (2).

[0019] Ice weight gain per unit area = ice weight gain ÷ sample surface area (1);

[0020] Surface ice reduction = (weight gain of ice layer per unit area of ​​steel substrate - weight gain of ice layer per unit area of ​​steel superhydrophobic surface) ÷ weight gain of ice layer per unit area of ​​steel substrate × 100% (2);

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] 1) The super-hydrophobic anti-icing surface of the present invention has a three-layer surface structure (such as Figure 1 As shown in the figure, in the chemical deposition layer, the deposition of copper constructs a rough surface structure, providing binding sites for low surface energy organic molecules, while copper can protect the innermost steel matrix; the low surface energy modification layer introduces hydrophobic organic molecules in the outermost layer of the anti-icing surface, giving the surface super-hydrophobic and anti-icing properties.

[0023] 2) Through the above preparation method, a super hydrophobic and anti-icing surface of steel can be obtained. Compared with the steel substrate, the surface can reduce the surface ice by more than 75%, has good anti-icing performance, and can also play a beneficial role in the anti-fouling and anti-corrosion of the steel surface. The preparation method of the super hydrophobic and anti-icing surface of steel is simple and efficient, and the raw materials used are cheap and easy to obtain. It is both economical and safe, and is conducive to large-scale industrial production. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 It is a schematic diagram of the structure of the super-hydrophobic and anti-icing surface of steel.

[0025] Figure 2 It is a flow chart for the preparation of superhydrophobic and anti-icing surface of steel. DETAILED DESCRIPTION

[0026] In order to make the purpose, technical solutions and advantages of the present invention more clearly understood, the specific implementation methods of the present invention are further described below in conjunction with embodiments. The following embodiments are used to specifically illustrate the contents of the present invention. These embodiments are only general descriptions of the contents of the present invention and do not limit the contents of the present invention.

[0027] Embodiment 1:

[0028] See Figure 1 , Figure 2 , the method of the present invention is used to prepare the super-hydrophobic and anti-icing surface of ship plate steel A plate. The surface of the A plate is deoiled, degreased, and cleaned with deionized water, and then polished to 1200 mesh with water sandpaper. Using 0.05 mol / L copper sulfate solution as the chemical deposition liquid, the steel sample after surface pretreatment is chemically deposited for 100s. After deposition, it is successively cleaned with deionized water, ultrasonically cleaned, and cleaned with ethanol. The steel surface after chemical deposition is modified with 0.05 mol / L stearic acid ethanol solution for 60 min. The modified steel sample is cleaned with ethanol and dried at 20°C to obtain the super-hydrophobic and anti-icing surface of the ship plate steel A plate, with a water contact angle of 155.4° and a surface ice reduction of 75.15%.

[0029] Embodiment 2:

[0030] See Figure 1 , Figure 2 , the method of the present invention is used to prepare the Q420qD super-hydrophobic steel surface of bridge steel. The Q420qD surface is degreased, degreased, and cleaned with deionized water, and then polished to 200 mesh with water sandpaper. Using 0.1 mol / L copper chloride solution as the chemical deposition liquid, the steel sample after surface pretreatment is chemically deposited for 10 seconds. After deposition, it is successively cleaned with deionized water, ultrasonically cleaned, and cleaned with ethanol; the steel surface after chemical deposition is modified with 0.01 mol / L methyltrimethoxysilane ethanol solution for 10 min; the modified steel sample is cleaned with ethanol and dried at 80°C to obtain a Q420qD super-hydrophobic steel surface with a water contact angle of 158.1° and a surface ice reduction of 81.10%.

[0031] Embodiment 3:

[0032] See Figure 1 , Figure 2, the method of the present invention is used to prepare the super-hydrophobic steel surface of marine steel VL4-4. The surface of VL4-4 is deoiled, degreased, cleaned with deionized water, and polished to 800 mesh with water sandpaper. Using 0.001 mol / L copper sulfate solution as chemical deposition liquid, the steel sample after surface pretreatment is chemically deposited for 500s. After deposition, it is successively cleaned with deionized water, ultrasonically cleaned, and cleaned with ethanol; 0.1 mol / L perfluorodecyltrimethoxysilane acetone solution is used to modify the steel surface after chemical deposition for 120 min; the modified steel sample is cleaned with ethanol and dried at 50°C to obtain a VL4-4 super-hydrophobic steel surface with a water contact angle of 161.8° and a surface ice reduction of 84.32%.

Claims

1. A method for preparing a steel super-hydrophobic anti-icing surface based on chemical deposition, characterized in that: A rough structure is constructed on the steel surface by chemical deposition, and then a low surface energy modification is performed to obtain a super hydrophobic and anti-icing surface of the steel. The preparation process is: surface pretreatment → chemical deposition → low surface energy modification → cleaning and drying, specifically including: 1) Chemical deposition: The steel sample is placed in a chemical deposition solution for chemical deposition, wherein the deposition solution is composed of salt and water, wherein the salt component is a copper salt, the salt concentration is 0.001 to 0.1 mol / L, and the deposition time is 10 to 500 s; 2) Low surface energy modification: The steel surface after chemical deposition is modified by using a modifier, wherein the modifier is composed of a low surface energy substance and an organic solvent, the concentration of the low surface energy substance in the modifier is 0.01 to 0.1 mol / L, and the modification time is 10 to 120 min; The copper salt is copper chloride or copper sulfate, which is washed with deionized water, ultrasonically cleaned, and then with ethanol after deposition; The low surface energy substance comprises at least one of fatty acid substances, oxygen silane substances, fluorosilane substances, and thiol substances, and the solvent is at least one of ethanol and acetone; The fatty acid substances include stearic acid, myristic acid, perfluorooctanoic acid, and palmitic acid; the oxygen silane substances include methyltrimethoxysilane, vinyltrimethoxysilane, and hexadecyltrimethoxysilane; the fluorosilane substances include perfluorodecyltrimethoxysilane and perfluorooctyltrichlorosilane; the thiol substances include dodecyl mercaptan and perfluorodecyl mercaptan; The surface pretreatment method includes: degreasing, degreasing, and cleaning the surface of the steel sample with deionized water, and polishing the surface with water sandpaper to 200-1200 mesh; The cleaning and drying method comprises: cleaning and drying the modified steel sample with ethanol at a drying temperature of 20 to 80°C; Under the same service environment, the steel superhydrophobic anti-icing surface reduces surface ice coverage by more than 75% compared to the steel substrate.

2. A super hydrophobic anti-icing surface of steel based on chemical deposition, characterized in that: It is prepared by the preparation method of the steel super-hydrophobic anti-icing surface based on chemical deposition as described in claim 1, and the steel super-hydrophobic anti-icing surface includes a steel substrate, a heterogeneous metal deposition layer and a low surface energy material layer, which has a three-layer surface structure, and the static contact angle between the surface and water is greater than 150°.

3. The chemically deposited steel super-hydrophobic anti-icing surface according to claim 2, characterized in that: The steel substrate is low alloy steel; the heterogeneous metal deposition layer is a copper deposition layer; the low surface energy substance includes at least one of fatty acid substances, oxygen silane substances, fluorosilane substances, and thiol substances.

4. The chemically deposited steel super-hydrophobic anti-icing surface according to claim 3, characterized in that: The steel substrate includes shipbuilding steel, bridge steel and marine engineering steel.

5. The chemically deposited steel super-hydrophobic anti-icing surface according to claim 2, characterized in that: Under the same service environment, the steel superhydrophobic anti-icing surface reduces surface ice coverage by more than 75% compared to the steel substrate.

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