Super-hydrophobic copper layer and method for preparing the same

Abstract

The present application relates to the technical field of metal material surface treatment, and particularly relates to a super-hydrophobic copper layer and a preparation method thereof. The present application discloses a preparation method of a super-hydrophobic copper layer, comprising the following steps: taking brass alloy as a substrate, placing the substrate in an acid solution to remove oxides and oil stains on the surface of the substrate; placing the substrate into a formamide aqueous solution to soak, and constructing a layer of nano-flower structure on the surface thereof; immersing the substrate into a saturated copper sulfate solution to perform chemical plating; placing the substrate into a mixed plating solution of copper sulfate, nickel sulfamate and silicon dioxide nanoparticles to perform electrochemical deposition; and immersing the substrate into a mixed aqueous solution of silane coupling agent, phosphoric acid and metavanadate to obtain a super-hydrophobic copper layer. The present application constructs a multi-dimensional structure on the surface of the substrate, and the super-hydrophobicity is enhanced, so that the present application has a broad application prospect.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of metal material surface treatment, in particular to a super-hydrophobic copper layer and a preparation method thereof. BACKGROUND

[0002] Due to the excellent electrical conductivity, thermal conductivity, certain strength and good processability of copper and copper alloy, and the good alloying ability, the copper and copper alloy meet the requirements of modern engineering field on material strength, toughness, wear resistance and other special properties, and are widely used in various industries. However, the copper metal has high activity and is easy to be corroded, which seriously deteriorates the thermal and electrical conductivity of copper.

[0003] In recent years, the application of the super-hydrophobic surface is more and more widely, and the super-hydrophobic surface is widely used in fabric, metal surface protection and other aspects. In the aspect of metal corrosion protection, the research on the super-hydrophobic surface has been widely applied to common metal substrates such as copper, aluminum and iron.

[0004] The wettability of an object is usually measured by the standard of "contact angle". The contact angle refers to the angle between the tangent of the gas-liquid interface at the gas-liquid-solid three-phase contact point and the solid-liquid interface.

[0005] Inspired by the lotus effect, the super-hydrophobic surface with a water contact angle greater than 150° has attracted widespread attention. On the super-hydrophobic surface, the liquid drop with water as the solvent usually forms a spherical shape, and the liquid drop will roll off the super-hydrophobic surface when the super-hydrophobic surface is slightly inclined at a certain angle, and cannot stably stay on the super-hydrophobic surface. Therefore, the chemical reaction and electrochemical reaction with water as the medium are maximally inhibited on the super-hydrophobic surface, and thus the super-hydrophobic surface has the functions of corrosion prevention, prevention of current conduction and oxidation resistance.

[0006] The surface with hydrophobicity and super-hydrophobicity usually meets two conditions, one is the micro-nano composite structure, and the other is the low surface energy material. Directly attaching a layer of low surface energy substance on the surface can make the surface exhibit hydrophobicity, but for the surface with micro-nano structure, attaching the low surface energy substance will make it more inclined to composite wetting, so as to further increase the contact angle of the surface. Therefore, the process of how to manufacture uniform nano structure on the non-uniform micron structure is particularly crucial. SUMMARY

[0007] In order to solve the above technical problems in the prior art, the present application provides a preparation method of a super-hydrophobic copper layer, comprising the following steps:

[0008] Step 1, taking brass alloy as a substrate, placing the substrate in an acid solution to remove the oxides and oil stains on the surface of the substrate;

[0009] Step 2, the substrate treated in step 1 is soaked in a formamide aqueous solution to construct a layer of nanoflower structure on the surface of the substrate; Step 3, the substrate treated in step 2 is immersed in a saturated copper sulfate solution for chemical plating;

[0010] Step 4, the substrate treated in step 3 is placed in a mixed plating solution of copper sulfate, nickel sulfamate and silica nanoparticles for electrochemical deposition;

[0011] Step 5, the substrate treated in step 4 is soaked in a mixed aqueous solution of silane coupling agent, phosphoric acid and metavanadate to obtain the super-hydrophobic copper layer.

[0012] The present application uses chemical plating and electrochemical deposition methods to jointly form a super-hydrophobic copper layer with a multi-dimensional structure on the surface of brass alloy, and the obtained super-hydrophobic copper layer has a water contact angle greater than 150°, and the super-hydrophobicity is enhanced, which has a wide application prospect.

[0013] Further, in step 1, the acid solution is a dilute acid solution with a volume concentration of 8%-12%.

[0014] Further, in step 2, the volume ratio of the formamide aqueous solution is 40-60%, the soaking time is 24-48h, and the temperature is room temperature.

[0015] Further, in step 3, the concentration of the saturated copper sulfate is 70-100g / L, the reaction time is 8-15min, and the temperature is 40℃-60℃.

[0016] Further, in step 4, in the mixed plating solution, the concentration ratio of copper sulfate to nickel sulfamate is 10:1, the addition amount of silica nanoparticles is 5-7g / L, the potential is set to 0.8V-2.3V, the current density is 1-5A / dm 2 , the reaction time is 30-60s, and the temperature is controlled to 40-55℃.

[0017] Further, the concentration of copper sulfate is 50-90g / L, and the concentration of nickel sulfamate is 5-9g / L.

[0018] Further, in step 5, the sum of the volume concentrations of the silane coupling agent, phosphoric acid and metavanadate is 2%, the reaction time is 1-3min, and the temperature is room temperature.

[0019] Further, the volume concentration of the silane coupling agent is not less than 0.8%, the volume concentration of the phosphoric acid is not less than 0.55%, and the volume concentration of the metavanadate is not less than 0.1%.

[0020] Further, the silane coupling agent is selected from the amino functional group series.

[0021] Further, the silane coupling agent is selected from any one of N-(2-aminoethyl)-3- aminopropylmethyldimethoxysilane, 3-aminopropyltrimethoxysilane, N-phenyl-3- aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane.

[0022] Further, the metavanadate is selected from any one of ammonium metavanadate, sodium metavanadate, potassium metavanadate.

[0023] Further, the copper content in the brass alloy is 90%, and the zinc content is 10%.

[0024] The application further provides an ultrahydrophobic copper layer prepared by the preparation method.

[0025] Compared with the prior art, the application has the following technical effects:

[0026] The application places the substrate into the aqueous formamide solution, and the substrate surface self-assembles to generate a flower-shaped three-dimensional structure of Cu(OH)2·H2O nanosheet aggregation; in the presence of formamide, the presence of oxygen promotes the oxidation of copper to dissolve Cu 2+ into the solution, and formamide immediately coordinates with the generated Cu 2+ to form [Cu(HCONH2)4] 2+ complex, which reacts with OH- to form a three-dimensional nanoflower structure of copper (II) hydroxide on the substrate surface for subsequent electroless plating treatment;

[0027] The substrate surface with the three-dimensional nanoflower structure is subjected to electroless plating treatment by a saturated aqueous copper sulfate solution to form a multidimensional copper plating layer, so that the hydrophobicity of the substrate surface is greatly increased; then, an anticorrosion alloy rust-proof layer is formed through electrochemical deposition; finally, a silane coupling agent layer is formed on the anticorrosion alloy rust-proof layer, and other substances and the silane coupling agent produce a synergistic effect to enhance the corrosion resistance; wherein the multidimensional copper plating layer structure refers to a copper plating layer in a spherical or hollow spherical or flower-shaped structure.

[0028] The application changes the material surface energy and micro roughness of the copper surface, systematically adjusts the hydrophobicity of the surface, and enhances the surface hydrophobicity, so as to reduce the contact with the external corrosion medium, form a shielding effect, and produce excellent corrosion resistance. DETAILED DESCRIPTION

[0029] The advantages and effects of the present application can be easily understood by those skilled in the art from the content disclosed in the specification. Although the description of the present application will be introduced in combination with the preferred embodiments, it does not mean that the features of the present application are limited to the embodiments. On the contrary, the purpose of introducing the present application in combination with the embodiments is to cover other options or modifications that can be extended based on the claims of the present application. In order to provide a deep understanding of the present application, many specific details will be included in the following description. The present application can also be implemented without using these details. In addition, in order to avoid confusion or ambiguity of the present application, some specific details will be omitted in the description. It should be noted that the embodiments in the present application and the features in the embodiments can be combined with each other without conflict.

[0030] Embodiment 1

[0031] A preparation method of forming a super-hydrophobic copper layer with a multi-dimensional structure on the surface of a brass alloy, comprising the following steps:

[0032] Step 1: Put the substrate into a dilute nitric acid solution with a volume concentration of 10% for soaking to remove the oxides and oil stains on the surface;

[0033] Step 2: Put the substrate treated in step 1 into a formamide aqueous solution for soaking to build a layer of nano-flower structure on the surface, the volume ratio of the formamide aqueous solution is 40%, the soaking time is 36h, and the temperature is room temperature;

[0034] Step 3: Put the substrate treated in step 2 into a saturated copper sulfate solution for chemical plating, the concentration of the saturated copper sulfate is 70g / L, the reaction time is 14min, and the temperature is 40℃;

[0035] Step 4: Electrochemically deposit the substrate treated in step 3 in a mixed plating solution of copper sulfate, nickel sulfamate and silica nanoparticles, the concentration of copper sulfate is 55g / L, the concentration of nickel sulfamate is 5.5g / L, the addition amount of silica nanoparticles is 6g / L, the potential is set to 1.2V, the current density is 1.5A / dm 2 , the reaction time is 60min, and the temperature is 40℃;

[0036] Step 5: Soak the substrate obtained in step 4 in a mixed aqueous solution of N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, phosphoric acid and ammonium metavanadate, the volume fractions of N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, phosphoric acid and ammonium metavanadate are 0.98%, 0.92% and 0.1% respectively, the reaction time is 2min, and the temperature is room temperature.

[0037] Embodiment 2

[0038] Step 1: The substrate is immersed in a dilute sulfuric acid solution with a volume concentration of 8% to remove surface oxides and oil stains;

[0039] Step 2: The substrate treated in Step 1 is immersed in a formamide aqueous solution to build a layer of nanoflower structure on its surface, the formamide aqueous solution has a volume ratio of 60%, the immersion time is 26h, and the temperature is room temperature;

[0040] Step 3: The substrate treated in Step 2 is immersed in a saturated copper sulfate solution for chemical plating, the concentration of saturated copper sulfate is 100g / L, the reaction time is 9min, and the temperature is 60℃;

[0041] Step 4: The substrate treated in Step 3 is subjected to electrochemical deposition in a mixed plating solution of copper sulfate, nickel sulfamate, and silica nanoparticles, the concentration of copper sulfate is 88g / L, the concentration of nickel sulfamate is 8.8g / L, the addition amount of silica nanoparticles is 5g / L, the potential is set to 2V, the current density is 3A / dm 2 , the reaction time is 40s, and the temperature is 50℃;

[0042] Step 5: The substrate obtained in Step 4 is immersed in a mixed aqueous solution of 3-aminopropyltrimethoxysilane, phosphoric acid, and ammonium metavanadate, the volume fractions of 3-aminopropyltrimethoxysilane, phosphoric acid, and ammonium metavanadate are 1.2%, 0.55%, and 0.25% respectively, the reaction time is 3min, and the temperature is room temperature.

[0043] Example 3

[0044] Step 1: The substrate is immersed in a dilute sulfuric acid solution with a volume concentration of 12% to remove surface oxides and oil stains, etc.

[0045] Step 2: The substrate treated in Step 1 is immersed in a formamide aqueous solution to build a layer of nanoflower structure on its surface, the formamide aqueous solution has a volume ratio of 50%, the immersion time is 40h, and the temperature is room temperature;

[0046] Step 3: The substrate treated in Step 2 is immersed in a saturated copper sulfate solution for chemical plating, the concentration of saturated copper sulfate is 83g / L, the reaction time is 12min, and the temperature is 50℃;

[0047] Step 4: The substrate treated in Step 3 is subjected to electrochemical deposition in a mixed plating solution of copper sulfate, nickel sulfamate, and silica nanoparticles, the concentration of copper sulfate is 70g / L, the concentration of nickel sulfamate is 7g / L, the addition amount of silica nanoparticles is 7g / L, the potential is set to 0.8V, the current density is 5A / dm 2 , the reaction time is 30s, and the temperature is 45℃;

[0048] Step 5: The substrate obtained in step 4 was immersed in a mixed aqueous solution of N-phenyl-3-aminopropyltrimethoxysilane, phosphoric acid and ammonium metavanadate with concentrations of 0.8%, 0.6% and 0.6% volume fraction, respectively, for 1 min at room temperature.

[0049] Comparative Example

[0050] Brass alloy surface without this surface treatment.

[0051] Static contact angle tests were performed on the samples of Examples 1-3 and the comparative example.

[0052] Static contact angles were measured using a Shanghai Zhongchen JC-2000C1 instrument, and the results are shown in Table 1.

[0053] Table 1. Results of static contact angle tests

[0054] Static contact angle Example 1 155.2° Example 2 156.8° Example 3 154.6° Comparative Example 85°

[0055] The above description is merely preferred embodiments of the present application, and is not intended to limit the present application. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A method for preparing a superhydrophobic copper layer, characterized in that, The method comprises the following steps: Step 1, taking brass alloy as a substrate, placing the substrate in an acid solution to remove the oxide and oil stain on the surface of the substrate; Step 2, placing the substrate treated in step 1 into a formamide aqueous solution to soak, and constructing a layer of nano-flower structure on the surface of the substrate; Step 3, immersing the substrate treated in step 2 into a saturated copper sulfate solution for chemical plating; Step 4, the substrate treated in step 3 is placed in a mixed plating solution of copper sulfate, nickel sulfamate and silica nanoparticles for electrochemical deposition, the potential is set to 0.8-2.3 V, the current density is 1-5 A / dm 2 , the reaction time is 30-60 s, the temperature is controlled to 40-55℃, in the mixed plating solution, the concentration ratio of copper sulfate to nickel sulfamate is 10:1, and the addition amount of silica nanoparticles is 5-7 g / L; Step 5, immersing the substrate treated in step 4 into a mixed aqueous solution of silane coupling agent, phosphoric acid and metavanadate to obtain the super-hydrophobic copper layer.

2. The method of claim 1, wherein the method is characterized by, In step 2, the volume ratio of the formamide aqueous solution is 40-60%, the soaking time is 24-48h, and the temperature is room temperature.

3. The method of claim 1, wherein the method further comprises the step of applying a layer of a hydrophobic material to the surface of the copper layer. In step 3, the concentration of the saturated copper sulfate is 70-100g / L, the reaction time is 8-15min, and the temperature is 40-60℃.

4. The method of claim 1, wherein the method is characterized by, The concentration of the copper sulfate is 50-90g / L, and the concentration of the nickel sulfamate is 5-9g / L.

5. The method of claim 1, wherein the superhydrophobic copper layer is prepared by the steps of: In step 5, the sum of the volume concentrations of the silane coupling agent, phosphoric acid and metavanadate is 2%, the reaction time is 1-3min, and the temperature is room temperature.

6. The method of claim 5, wherein the method further comprises: The volume concentration of the silane coupling agent is not less than 0.8%, the volume concentration of the phosphoric acid is not less than 0.55%, and the volume concentration of the metavanadate is not less than 0.1%.

7. The method of claim 1, wherein the superhydrophobic copper layer is prepared by the steps of: The silane coupling agent is selected from an amino functional group series.

8. The method of claim 1, wherein the superhydrophobic copper layer is prepared by the steps of: The copper content in the brass alloy is 90%, and the zinc content is 10%.

9. A superhydrophobic copper layer, characterized in that, The super-hydrophobic copper layer is prepared by the preparation method in any one of claims 1-8.