CN110219005A - Copper-based material inhibiting solution and preparation method thereof, corrosion inhibition method - Google Patents

Abstract

A kind of copper-based material inhibiting solution and preparation method thereof, corrosion inhibition method, the inhibiting solution include that mass ratio is (1~100): (2~11): 1000 hydrophobically modified nanoparticle, corrosion inhibiter and organic solvent.A kind of slow rotten method is also provided, an air boundary is formed between copper-based material surface, the microstructure and corrosion inhibiter of hydrophobically modified nanoparticle surface by spraying above-mentioned inhibiting solution, while playing corrosion inhibition, does not influence copper-based electric conductivity.

Description

Corrosion inhibitor solution for copper-based materials, preparation method thereof, and corrosion inhibition method

technical field

The invention belongs to the technical field of corrosion and protection of copper-based materials, and in particular relates to a corrosion-inhibiting solution for copper-based materials, a preparation method thereof, and a corrosion-inhibiting method.

Background technique

Copper is one of the earliest metal materials used by humans. Pure copper (copper) has good ductility, thermal conductivity and electrical conductivity, and is widely used in electrical, light industry, machinery manufacturing and other fields. In order to obtain better copper materials with specific properties, elements such as silicon and zinc are often added to it to obtain a series of copper-based materials.

An important characteristic of copper-based materials is electrical conductivity, but in the natural atmospheric state, copper can oxidize with oxygen in the air and affect its electrical contact performance. In order to prevent the copper-based oxidation process, a surface protection treatment is generally required. Because most of the coatings formed by conventional coatings use resin film formers, the coatings are thick and non-conductive, and there are obvious deficiencies in the application fields that do not want to change the conductivity of copper-based materials.

Contents of the invention

In view of this, the main purpose of the present invention is to provide a copper-based material corrosion inhibitor, its preparation method, and corrosion inhibition method, in order to at least partially solve at least one of the above-mentioned technical problems.

As one aspect of the present invention, a corrosion inhibitor solution for copper-based materials is provided, including hydrophobically modified nanoparticles with a mass ratio of (1-100):(2-11):1000, a corrosion inhibitor and an organic solvent.

As another aspect of the present invention, there is provided a method for preparing the corrosion inhibitor solution for copper-based materials as described above, comprising the following steps:

Grinding and dispersing the hydrophobically modified nanoparticles into an organic solvent to obtain a dispersion, wherein the mass ratio of the hydrophobically modified nanoparticles to the organic solvent is 1:10 to 1:1000;

The corrosion inhibitor is added to the dispersion to obtain the copper-based material corrosion inhibitor, wherein the mass ratio of the corrosion inhibitor to the dispersion is 1:100-1:500.

As another aspect of the present invention, a method for inhibiting corrosion of copper-based materials is provided, comprising the following steps:

Spraying the above-mentioned copper-based material corrosion inhibitor solution on the surface of the copper-based material to form a corrosion-inhibiting layer on the surface of the copper-based material;

Wherein, the corrosion inhibition layer includes hydrophobically modified nanoparticles dispersed on the surface of the copper-based material, a corrosion inhibitor adsorbed on the surface of the copper-based material, and an air interface layer formed between the hydrophobically modified nanoparticles and the corrosion inhibitor .

As another aspect of the present invention, a conductive material is provided, comprising:

Copper-based materials; and

The corrosion inhibition layer includes hydrophobically modified nanoparticles dispersed on the surface of the copper-based material, a corrosion inhibitor adsorbed on the surface of the copper-based material, and an air interface layer formed between the hydrophobically modified nanoparticles and the corrosion inhibitor.

As yet another aspect of the present invention, an application of the above-mentioned conductive material in electrical contact components is provided.

Based on above-mentioned technical scheme, the advantage of the present invention is:

(1) The modified nanoparticles provided by the invention have a particle size of 20-200nm, good monodispersity, certain surface microstructure, high surface activity, and a small amount of nano-dispersion on the copper-based surface, which can promote the corrosion inhibitor in the copper-based material. A corrosion-inhibiting layer is quickly formed on the surface to improve the corrosion-inhibiting effect of the corrosion inhibitor.

(2) The corrosion inhibitor solution for copper-based materials provided by the present invention can be directly sprayed on the surface of copper-based materials and parts, and an air interface layer is formed between the microstructure of the modified nanoparticle surface and the corrosion inhibitor, which can play a role in slowing down Corrosion effect, the formed corrosion inhibition layer is very thin and does not affect the conductivity of the copper base, and at the same time provides a certain protective effect.

Description of drawings

Fig. 1 (a) is the hydrophobically modified SiO that the embodiment of the present invention ₁ prepares Nanoparticle microscopic topography scanning electron microscope picture;

Fig. 1 (b) is the hydrophobically modified SiO prepared by the embodiment of the present invention ₁ Nanoparticles Fourier transform infrared spectrum (FTIR) figure;

Fig. 2 is a schematic diagram of the dispersion of hydrophobically modified nanoparticles with surface microstructure in the present invention on the copper-based surface;

Fig. 3 is the hydrophobically modified SiO prepared by the embodiment of the present invention ₁ Nanoparticles promote the adsorption of corrosion inhibitor open circuit potential-time diagram;

Fig. 4 (a) is the electrochemical impedance curve (EIS) of the H62 brass before and after the embodiment of the present invention 1 utilizes corrosion inhibitor treatment;

Fig. 4 (b) is the electrochemical impedance curve (EIS) fitting equivalent circuit of the H62 brass after the embodiment of the present invention 1 utilizes corrosion inhibitor treatment;

Fig. 5 is the Tafel (Tafel) curve of the H62 brass before and after the corrosion inhibitor treatment of embodiment 1 of the present invention;

Fig. 6 is the microscopic morphology and wetting angle measurement diagram of H62 brass surface after different times of corrosion inhibitor spraying treatment in Example 1 of the present invention (0 time, 1 time, 5 times, 10 times, 15 times, 20 times).

In the above accompanying drawings, the meanings of the reference signs are as follows:

1-copper-based material; 2-corrosion medium; 3-hydrophobic modified nanoparticles;

4-corrosion inhibitor; 5-air interface layer.

Detailed ways

In order to make the object, technical solution and advantages of the present invention clearer, the present invention will be further described in detail below in conjunction with specific embodiments and with reference to the accompanying drawings.

The invention uses hydrophobic modified nanoparticles and corrosion inhibitors to prepare a dispersion liquid, and directly sprays on the surface of the copper-based material to realize rapid and synergistic protection without affecting the conductivity of the copper-based material. It is further dispersed with an environmentally friendly solvent ethanol and sprayed for use. It is also possible to control the number of sprays to make the surface of the copper-based material hydrophobic.

According to some embodiments of the present invention, a corrosion inhibitor solution for copper-based materials is provided, comprising hydrophobically modified nanoparticles, a corrosion inhibitor and a solvent in a mass ratio of (1-100):(2-11):1000. When a small amount of hydrophobic modified nanoparticles are dispersed on the surface of copper-based materials, it can promote the rapid and uniform adsorption of corrosion inhibitors on the surface of copper-based materials; using the microstructure of the surface of modified nanoparticles and corrosion inhibitors to form an air interface layer, without affecting copper While improving the conductivity of the base, it also acts as a barrier to corrosive media, thereby improving the protection of copper-based materials. The air interface layer can slow down electrochemical corrosion, including corrosion in humid environment, seawater environment, acidic or alkaline medium environment.

Preferably, the hydrophobically modified nanoparticles have a particle diameter of 20-200 nm, and are hydrophobically modified SiO ₂ nanoparticles, TiO ₂ nanoparticles, Al ₂ O ₃ nanoparticles or ZnO nanoparticles. If the amount of the hydrophobically modified nanoparticles is too much, it will accumulate on the surface of the copper-based material, which will affect the physical and chemical properties of the substrate surface, such as the electrical connection characteristics of the copper-based material; if the amount is too small, it will not work, and cannot provide auxiliary adsorption and improve The role of corrosion inhibition.

Preferably, the hydrophobically modified nanoparticles are prepared by hydrophobically modifying the nanoparticles with a silane coupling agent or a C6-C10 linear alcohol as a modifier; wherein the silane coupling agent is, for example, phenyltriethoxysilane , Hexadecyltrimethoxysilane, Dodecyltrimethoxysilane, γ-Methacryloxypropyltrimethoxysilane (KH-570) or Vinyltriethoxysilane.

Preferably, the corrosion inhibitor is benzotriazole, triazole derivatives or 2-mercaptobenzoxazole.

Preferably, the organic solvent is toluene or ethanol.

According to some embodiments of the present invention, there is also provided a method for preparing the above copper-based material corrosion inhibitor solution, comprising the following steps:

Grinding and dispersing the hydrophobically modified nanoparticles into an organic solvent to obtain a dispersion, wherein the mass ratio of the hydrophobically modified nanoparticles to the organic solvent is 1:10 to 1:1000;

The corrosion inhibitor is added to the dispersion to obtain the copper-based material corrosion inhibitor, wherein the mass ratio of the corrosion inhibitor to the dispersion is 1:100-1:500.

Preferably, the hydrophobically modified nanoparticles can be prepared, for example, by the following steps:

Adding a nanoparticle precursor to solution A comprising a base and a solvent to obtain solution B;

Add a modifying agent to the solution B, heat and stir for 12-24 hours, centrifuge and dry to obtain hydrophobically modified nanoparticles.

Specifically, the nanoparticle precursors are, for example, silicate, titanate, zinc salt or aluminum salt, etc., which are used to prepare hydrophobically modified _SiO2 nanoparticles, _TiO2 nanoparticles, _{Al2O3 nanoparticles} or ZnO nanoparticles, etc. Of course, the preparation method of the hydrophobic nanoparticles is not limited to this, and other known methods can also be used for preparation.

According to some embodiments of the present invention, a method for inhibiting corrosion of copper-based materials is also provided, comprising the following steps:

The above-mentioned copper-based material corrosion inhibitor solution is sprayed on the surface of the copper-based material to form a corrosion-inhibited layer on the surface of the copper-based material; wherein, the corrosion-inhibited layer includes hydrophobically modified nanoparticles dispersed on the surface of the copper-based material, The corrosion inhibitor on the surface and the air interface layer formed between the hydrophobically modified nanoparticles and the corrosion inhibitor.

Preferably, the number of times of spraying is 1 to 15 times, and as the number of times of spraying increases, the hydrophobic performance of the surface of the copper-based material is better, which is beneficial to hinder the corrosion inhibiting medium.

According to some embodiments of the present invention, a conductive material treated by the above corrosion inhibition method is also provided, including:

Copper-based materials; and

The corrosion inhibition layer includes hydrophobically modified nanoparticles dispersed on the surface of the copper-based material, a corrosion inhibitor adsorbed on the surface of the copper-based material, and an air interface layer formed between the hydrophobically modified nanoparticles and the corrosion inhibitor.

According to some embodiments of the present invention, there is also provided an application of the above-mentioned conductive material in the field of electrical contact, such as electrical contact components.

The present invention will be further illustrated by comparative examples, examples and relevant test experiments below. In the following detailed description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of the embodiments of the invention. It may be evident, however, that one or more embodiments may be practiced without these specific details. Moreover, in the case of no conflict, the details in the following embodiments can be combined arbitrarily into other feasible embodiments.

Example 1:

Preparation of corrosion inhibitor solution for copper-based materials:

A copper-based material corrosion inhibitor, the specific preparation steps are as follows:

In the first step, add 5g of deionized water and 1g of ammonia water to 50g of ethanol, stir for 15 minutes, make it evenly mixed, and obtain solution A;

In the second step, add the mixed solution A into a three-neck flask with a condenser, add 3.5 g of tetraethyl orthosilicate to solution A, and stir rapidly at room temperature for 20 minutes to obtain solution B;

In the third step, 0.4 g of nano-SiO ₂ modifier-phenyltriethoxysilane (PTES) was slowly added dropwise to solution B, and stirring was continued for 18 hours at room temperature. After the reaction, the product was centrifugally washed and dried to hydrophobically modify the SiO ₂ nanoparticles.

Step ₄ : Grind 0.1g of hydrophobically modified SiO nanoparticles and disperse them in 100g of ethanol to prepare dispersion D;

Step 5: Add 0.5 g of benzotriazole (BTA) to the above dispersion D to prepare a corrosion inhibitor solution for copper-based materials.

Performance test: The particle size of the hydrophobically modified SiO ₂ nanoparticles was measured by a Malvern Zetasizer Nano particle size potentiometer to be 100±25nm; the surface morphology of the hydrophobically modified SiO ₂ nanoparticles was investigated using a scanning electron microscope (JSM-7500F scanning electron microscope in Japan). Observation, the result is shown in Figure 1 (a), the surface of the hydrophobically modified SiO ₂ nanoparticles has a microscopically rough multi-level structure, and the monodispersity is good. The FTIR infrared spectrum of the hydrophobically modified _SiO2 nanoparticles is shown in Fig. 1(b), with the presence of Si-phenyl groups, proving the successful grafting.

Corrosion inhibition methods for copper-based materials:

Spray the above copper-based material corrosion inhibitor once on the H62 brass surface to form a corrosion inhibition layer. As shown in Figure 2, the corrosion inhibition layer includes hydrophobically modified nanoparticles 3 dispersed on the surface of the copper-based material 1, a corrosion inhibitor 4 adsorbed on the surface of the copper-based material, and between the hydrophobically modified nanoparticles 3 and the corrosion inhibitor 4. The air interface layer 5 formed between them can form a barrier to the corrosive medium 2 such as fresh water, sea water, acidic or alkaline medium, etc. Fig. 3 is the open circuit potential-time diagram of the promoting action of hydrophobically modified _SiO2 nanoparticles prepared by Example 1 of the present invention to the adsorption of corrosion inhibitors, as can be seen, the brass open circuit potential of spraying hydrophobically modified _SiO2 nanoparticles changes more rapidly Faster, and the degree is greater, indicating that spraying modified SiO ₂ nanoparticles can promote the adsorption of corrosion inhibitors.

Electrochemical performance tests were carried out on H62 brass without corrosion inhibition treatment and H62 brass sprayed with copper-based material corrosion inhibitor once. Using a three-electrode system, a saturated calomel electrode was used as a reference electrode, and a platinum sheet was used as an auxiliary electrode. Shanghai Chenhua Electrochemical Workstation CHI 660e was used for electrochemical tests; the AC impedance (EIS) was under (open circuit potential) OCP, the frequency range was 100kHz-0.01Hz, 5mV/s; the Tafel voltage range was OCP±300mV, 5mV/s. Fig. 4 (a) is the electrochemical AC impedance curve of the H62 brass before and after the corrosion inhibitor solution of the present invention is processed, adopts the circuit fitting of Fig. 4 (b), wherein Rs is solution resistance, Rc is surface film resistance, and Rt is air The interfacial layer resistance, CPEc and CPEd represent the capacitance of the surface film and the air interface layer, respectively. The results show that the air interface layer resistance Rt between the nanometer and the corrosion inhibitor is 3901Ω. Fig. 5 is the Tafel curve of the H62 brass before and after the corrosion inhibitor solution of the present invention is treated, and the result shows that after the corrosion inhibitor solution is treated, the corrosion current density Icorr of the brass surface is reduced to 0.74 μ A cm by ^4.27 μ A cm cm ^-2, . It is generally believed that a decrease in corrosion current indicates a decrease in corrosion rate, and the air interface layer between the nanometer and the corrosion inhibitor has a significant effect on improving corrosion inhibition. Dispersed nanoparticles basically do not affect the electrical conductivity of the brass surface. Use the JK2511 DC low resistance tester to test the surface resistance of the H62 brass before and after spraying the corrosion inhibitor solution, both of which are 0.08mΩ.

The DSA 20 video contact angle measuring instrument of Krüss Instruments GmbH in Germany was used to test the wetting angle of H62 brass after spraying corrosion inhibitor solution. The results are shown in Figure 6. With the increase of spraying times, the wetting angle increased from the original 89.2° to 133.2°, showing a certain hydrophobicity, indicating that the corrosion inhibitor treatment of the present invention can not only form corrosion protection As a result, it can also improve the hydrophobicity of the surface of the substrate.

Example 2:

Preparation of corrosion inhibitor solution for copper-based materials:

A copper-based material corrosion inhibitor, the specific preparation steps are as follows:

In the first step, add 6g of deionized water and 3g of ammonia water to 100g of ethanol, stir for 15 minutes, and mix them evenly to obtain solution A;

In the second step, add the mixed solution A into a three-neck flask with a condenser tube, add 4.5 g of ethyl orthosilicate to solution A, and stir rapidly at room temperature for 20 minutes to obtain solution B;

In the third step, slowly dropwise add 0.6 g of nano- _SiO2 modifier vinyltriethoxysilane to solution B, and continue stirring at room temperature for 12 hours. After the reaction, the product was centrifugally washed and dried to hydrophobically modify the SiO ₂ nanoparticles.

Step 4: Grind _2g of hydrophobically modified SiO nanoparticles and disperse them in 100g of ethanol to prepare dispersion D;

Step 5: Add 0.5g of benzotriazole (BTA) into the above-mentioned dispersion liquid D to prepare a corrosion inhibitor solution for copper-based materials;

Performance test: The particle size of the hydrophobically modified SiO ₂ nanoparticles was measured by a Malvern Zetasizer Nano particle size potentiometer to be 65±15nm.

Corrosion inhibition methods for copper-based materials:

Electrochemical performance tests similar to Example 1 were carried out on red copper without corrosion inhibition treatment and red copper sprayed with a copper-based material corrosion inhibitor once. The results showed that after the corrosion inhibitor treatment, the air interface layer resistance Rt was 3871Ω, The corrosion current density is reduced from 4.55μA·cm ^-2 to 0.54μA·cm ^-2 . The dispersed hydrophobically modified nanoparticles basically did not affect the electrical conductivity of the copper surface, and the JK2511 DC low resistance tester was used to test the surface resistance of the copper before and after spraying the corrosion inhibitor solution, both of which were 0.06mΩ.

The wetting angle test similar to that in Example 1 was carried out on the red copper after spraying the corrosion inhibitor treatment. As the number of spraying increases, the wetting angle can rise from the original 85.2° to 138.5°.

Example 3:

Preparation of corrosion inhibitor solution for copper-based materials:

A copper-based material corrosion inhibitor, the specific preparation steps are as follows:

In the first step, add 8 g of deionized water and 2.5 g of ammonia water to 100 g of ethanol, stir for 15 minutes, and mix them evenly to obtain solution A;

In the second step, add the mixed solution A into a three-necked flask with a condenser, add 5 g of tetraethyl orthosilicate to solution A, and stir rapidly at room temperature for 20 minutes to obtain solution B;

In the third step, slowly dropwise add 0.5 _g of nano-SiO modifier hexadecyltrimethoxysilane to solution B, and continue stirring at room temperature for 24 hours. After the reaction, the product was centrifugally washed and dried to hydrophobically modify the SiO ₂ nanoparticles.

Step ₄ : Grind 1.5g of hydrophobically modified SiO nanoparticles and disperse them in 100g of toluene to prepare dispersion D;

Step 5: Add 0.35g of 2-mercaptobenzoxazole (MBO) into the above-mentioned dispersion liquid D to prepare a corrosion inhibitor solution for copper-based materials;

Performance test: The particle size of the modified SiO ₂ nanoparticles was measured by a Malvern Zetasizer Nano particle size potentiometer to be 175±25nm.

Corrosion inhibition methods for copper-based materials:

The Cu-40Zn alloy without corrosion inhibition treatment and the Cu-40Zn alloy sprayed with a copper-based material corrosion inhibitor were tested for electrochemical performance similar to Example 1. The results showed that after the corrosion inhibitor treatment, the air interface The layer resistance Rt is 4650Ω, and the corrosion current density is reduced from 4.32μA·cm ^-2 to 0.48μA·cm ^-2 . The dispersed hydrophobically modified nanoparticles basically did not affect the surface conductivity of Cu-40Zn. The JK2511 DC low resistance tester was used to test the surface resistance of Cu-40Zn before and after spraying corrosion inhibitor treatment, both of which were 0.09mΩ.

The wetting angle test similar to that in Example 1 was carried out on the Cu-40Zn alloy treated by spraying the corrosion inhibitor. With the increase of the spraying times, the wetting angle increased from the original 88.9° to 142.3°.

Example 4:

Preparation of corrosion inhibitor solution for copper-based materials:

A copper-based material corrosion inhibitor, the specific preparation steps are as follows:

In the first step, add 6g of deionized water and 3g of ammonia water to 100g of ethanol, stir for 15 minutes, and mix them evenly to obtain solution A;

In the second step, add the mixed solution A into a three-neck flask with a condenser tube, add 4.5 g of ethyl orthosilicate to solution A, and stir rapidly at room temperature for 20 minutes to obtain solution B;

In the third step, slowly dropwise add 0.5 _g of nano-SiO modifier n-octanol to solution B, and continue to stir at room temperature for 12 hours. After the reaction, the product was centrifugally washed and dried to hydrophobically modify the SiO ₂ nanoparticles.

Step 4: Grind _2g of hydrophobically modified SiO nanoparticles and disperse them in 100g of ethanol to prepare dispersion D;

Step 5: Add 0.5g of benzotriazole (BTA) into the above-mentioned sub-dispersion D to prepare a copper-based material corrosion inhibitor;

Performance test: The particle size of the modified SiO ₂ nanoparticles was measured by a Malvern Zetasizer Nano particle size potentiometer to be 80±15nm.

Corrosion inhibition methods for copper-based materials:

The electrochemical performance test similar to Example 1 was carried out on the brass without corrosion inhibition treatment and the brass sprayed with the copper-based material corrosion inhibitor once. The results showed that after the corrosion inhibitor treatment, the air interface layer resistance Rt was 3959Ω, the corrosion current density is reduced from 4.27μA·cm ^-2 to 0.53μA·cm ^-2 . The dispersed hydrophobically modified nanoparticles basically did not affect the conductivity of the brass surface. The JK2511 DC low resistance tester was used to test the surface resistance of the brass before and after spraying the corrosion inhibitor treatment, and the surface resistance was 0.08mΩ.

Example 5:

Preparation of corrosion inhibitor solution for copper-based materials:

A copper-based material corrosion inhibitor, the specific preparation steps are as follows:

In the first step, add 5.5g of deionized water and 2g of ammonia water to 100g of ethanol, stir for 15 minutes, and mix them evenly to obtain solution A;

In the second step, add the mixed solution A into a three-necked flask with a condenser, add 5g of tetraethyl orthosilicate to solution A, and stir rapidly at room temperature for 20 minutes to obtain solution B; divide solution B into two parts , a part of which continued to be stirred for 12 hours by centrifugal washing and drying to obtain unmodified SiO ₂ nanoparticles, and the other part was carried out in step three.

In the third step, slowly dropwise add 0.5 g of nano- _SiO2 modifier phenyltriethoxysilane to solution B, and continue stirring at room temperature for 12 hours. After the reaction, the product was centrifugally washed and dried to modify the SiO ₂ nanoparticles.

Step 4: Grind _2g of unmodified and hydrophobically modified SiO nanoparticles separately, and then disperse them in 100g of ethanol to prepare dispersion D and dispersion F;

Step 5: Add 0.5g of benzotriazole (BTA) to the above-mentioned dispersion liquid D and dispersion liquid F respectively to prepare a copper-based material corrosion inhibitor;

Performance test: The particle size of the hydrophobically modified and unmodified SiO ₂ nanoparticles was measured by a Malvern Zetasizer Nano particle size potentiometer, both of which were 45±15nm.

Corrosion inhibition methods for copper-based materials:

Electrochemical performance tests were carried out on the brass sprayed with the copper-based material corrosion inhibitor containing unmodified _SiO2 nanoparticles and the brass sprayed with the copper-based material corrosion inhibitor containing hydrophobically modified _SiO2 nanoparticles. The results show that , after being treated with the copper-based material corrosion inhibitor solution containing unmodified _SiO2 nanoparticles, the interface resistance Rt between the hydrophobically modified nanoparticles and the corrosion inhibitor fitted by AC impedance spectroscopy is 1459Ω (due to the unmodified nanoparticle The surface of the particles is smooth, no obvious air interface layer is formed between the corrosion inhibitor and the Rt is small); the corrosion current density is changed from 4.27μA·cm ^-2 to 2.77μA·cm ^-2 , and the hydrophobically modified SiO ₂ After the corrosion inhibitor treatment, the interface resistance Rt of the air interface layer was 4145Ω, and the corrosion current density changed from 4.27μA·cm ^-2 to 0.87μA·cm ^-2 . Use the JK2511 type DC low resistance tester to test the surface resistance of the brass before and after spraying the corrosion inhibitor solution, and the surface resistance is 0.08mΩ.

Embodiment 6:

Preparation of corrosion inhibitor solution for copper-based materials:

A copper-based material corrosion inhibitor, the specific preparation steps are as follows:

In the first step, 5.8g of deionized water and 2.5g of ammonia water were added to 100g of ethanol, stirred for 15 minutes, and mixed evenly to obtain solution A;

In the second step, add the mixed solution A into a three-neck flask with a condenser tube, add 5 g of butyl titanate to the solution A, and stir rapidly at room temperature for 15 minutes to obtain a solution;

In the third step, slowly drop 0.75g of nano TiO ₂ modifier silane coupling agent KH-570 to solution B, and continue to stir at room temperature for 12 hours. After the reaction, the product was centrifugally washed and dried to modify the _{TiO2nanoparticles} .

Step 4: Grind 2g of hydrophobically modified _TiO2 nanoparticles separately, and then disperse them in 100g of ethanol to prepare dispersion D;

Step 5: Add 0.45g of benzotriazole (BTA) to the above-mentioned dispersion liquid D and dispersion liquid F respectively to prepare a copper-based material corrosion inhibitor;

Performance test: the particle size of the hydrophobically modified TiO ₂ nanoparticles was measured by a Malvern Zetasizer Nano particle size potentiometer, and the particle size was 25±5nm.

Corrosion inhibition methods for copper-based materials:

Electrochemical performance tests were carried out on brass sprayed with a copper-based material corrosion inhibitor containing hydrophobically modified _TiO2 nanoparticles. The results showed that after being treated with a hydrophobically modified _TiO2 corrosion inhibitor, the interface resistance Rt It is 4013Ω, and the corrosion current density is 0.79μA·cm ^-2 . Use the JK2511 type DC low resistance tester to test the surface resistance of the brass before and after spraying the corrosion inhibitor solution, and the surface resistance is 0.08mΩ.

The specific embodiments described above have further described the purpose, technical solutions and beneficial effects of the present invention in detail. It should be understood that the above descriptions are only specific embodiments of the present invention, and are not intended to limit the present invention. Within the spirit and principles of the present invention, any modifications, equivalent replacements, improvements, etc., shall be included in the protection scope of the present invention.

Claims (12)

1. a kind of copper-based material inhibiting solution is (1~100): (2~11) including mass ratio: 1000 hydrophobically modified nanoparticle, Corrosion inhibiter and organic solvent.

2. copper-based material inhibiting solution according to claim 1, which is characterized in that the hydrophobically modified nanoparticle is through dredging The modified SiO of water₂Nanoparticle, TiO₂Nanoparticle, Al₂O₃Nanoparticle or ZnO nanoparticle；

Preferably, the partial size of the hydrophobically modified nanoparticle is 20~200nm.

3. copper-based material inhibiting solution according to claim 1, which is characterized in that the hydrophobically modified nanoparticle is with silicon The straight chain alcohol of alkane coupling agent or C6~C10 are that nanoparticle hydrophobically modified is made in modifying agent；

Preferably, the silane coupling agent is phenyl triethoxysilane, hexadecyl trimethoxy silane, dodecyl three Methoxy silane, γ-methacryloxypropyl trimethoxy silane or vinyltriethoxysilane.

4. copper-based material inhibiting solution according to claim 1, which is characterized in that the corrosion inhibiter is benzotriazole, three Nitrogen Zole derivatives or 2- mercaptobenzoxazole.

5. copper-based material inhibiting solution according to claim 1, which is characterized in that the organic solvent is toluene or ethyl alcohol.

6. a kind of preparation method of the copper-based material inhibiting solution as described in claim 1 to 5 any one, comprising the following steps:

Hydrophobically modified nanoparticle is ground and is distributed in organic solvent, dispersion liquid is obtained, wherein the hydrophobically modified nanometer The mass ratio of particle and organic solvent is 1: 10~1: 1000；

Corrosion inhibiter is added in dispersion liquid, the copper-based material inhibiting solution is obtained, wherein the matter of the corrosion inhibiter and dispersion liquid Amount is than being 1: 100~1: 500.

7. preparation method according to claim 6, which is characterized in that the hydrophobically modified nanoparticle passes through following steps Preparation:

Nanoparticle precursor is added into the solution A comprising alkali and solvent, obtains solution B；

It is added modifying agent into solution B, and heating stirring 12~for 24 hours, it is centrifugated and is dried to obtain the hydrophobically modified nanometer Particle.

8. preparation method according to claim 7, it is characterised in that:

The nanoparticle precursor is esters of silicon acis, titanate esters, zinc salt or aluminium salt.

9. a kind of corrosion inhibition method of copper-based material, which comprises the following steps:

Copper-based material inhibiting solution as described in claim 1 to 5 any one is sprayed at copper-based material surface, described copper-based Material surface forms corrosion-inhibiting layer；

Wherein, the corrosion-inhibiting layer includes the hydrophobically modified nanoparticle for being scattered in copper-based material surface, is adsorbed in copper-based material table The corrosion inhibiter in face and the air boundary formed between the hydrophobically modified nanoparticle and corrosion inhibiter.

10. corrosion inhibition method according to claim 9, which is characterized in that spraying number is 1~15 time.

11. a kind of conductive material, comprising:

Copper-based material；And

Corrosion-inhibiting layer, including the hydrophobically modified nanoparticle for being scattered in copper-based material surface, the inhibition that is adsorbed in copper-based material surface Agent and the air boundary formed between the hydrophobically modified nanoparticle and corrosion inhibiter.

12. a kind of application of conductive material as claimed in claim 11 in electrical contact component.