CN112064080A

CN112064080A - Preparation method of sulfonated modified graphene oxide-based super-hydrophobic B30 copper-nickel alloy surface

Info

Publication number: CN112064080A
Application number: CN201910497163.8A
Authority: CN
Inventors: 陈宇
Original assignee: Binzhou University
Current assignee: Binzhou University
Priority date: 2019-06-10
Filing date: 2019-06-10
Publication date: 2020-12-11

Abstract

The invention belongs to the technical field of functional materials, and relates to a preparation method of a sulfonated modified graphene oxide-based super-hydrophobic B30 copper-nickel alloy surface. The invention provides a preparation method of a sulfonated modified graphene oxide-based super-hydrophobic B30 copper-nickel alloy surface, and particularly relates to a preparation method of a super-hydrophobic structure by adopting an electrodeposition method. Has the following advantages: on one hand, the B30 copper-nickel alloy surface rough structure is constructed by etching the B30 copper-nickel alloy in a linolenic acid medium, on the other hand, a chelate is formed by benzotriazole and copper, and the lamellar blocking function of the sulfonated modified graphene oxide is fully exerted by strong adsorption of the sulfonated modified graphene oxide on the copper surface, so that the super-hydrophobic B30 copper-nickel alloy has excellent corrosion resistance, the corrosion inhibition efficiency reaches more than 97%, and the super-hydrophobic B30 copper-nickel alloy has wide industrial application prospects.

Description

Preparation method of sulfonated modified graphene oxide-based super-hydrophobic B30 copper-nickel alloy surface

Technical Field

The invention belongs to the technical field of functional materials, and particularly relates to a preparation method of a sulfonated modified graphene oxide-based super-hydrophobic B30 copper-nickel alloy surface.

Background

With the wider application of the copper-nickel alloy B30 in national economy, particularly as an important component of a generator set-a condenser in China and other countries, most of the tubes of the copper-nickel alloy B30 are made of copper-nickel alloy, but are influenced by various factors, particularly Cl exists^-When the copper-nickel alloy pipe is corroded, the copper-nickel alloy pipe of the condenser is corroded, and the corrosion becomes a prominent problem whether the power plant can run safely and economically.

In recent years, inspired by the lotus effect, the super-hydrophobic surface with a contact angle of more than 150 degrees with a water drop has the strong hydrophobic characteristic that water molecules and corrosive ions are difficult to permeate into the super-hydrophobic surface, so that the corrosion resistance of the metal material is obviously improved.

At present, a super-hydrophobic structure is constructed on the surface of a metal material by the etching action of stearic acid on the metal material, but the super-hydrophobic structure has short service life and is easy to damage after being soaked in a corrosive medium for a long time. The preparation method of the super-hydrophobic surface reported at present either needs harsh equipment or has too long preparation time. Therefore, the preparation method for developing the simple, efficient and long-life super-hydrophobic B30 copper-nickel alloy surface has important economic and social significance.

Disclosure of Invention

Aiming at the problems in the prior art, the invention provides a method for preparing a sulfonated modified graphene oxide-based super-hydrophobic B30 copper-nickel alloy surface with high speed and long service life, and the super-hydrophobic structure constructed by the method is stable and is particularly suitable for protecting the B30 copper-nickel alloy in seawater corrosion medium.

The invention provides a preparation method of a sulfonated modified graphene oxide-based super-hydrophobic B30 copper-nickel alloy surface, which comprises the following steps:

(1) b30 copper-nickel alloy pretreatment:

b30 copper-nickel alloy is first polished with 60, 120, 320, 600 and 1200 mesh sand paper to eliminate surface impurity and oxide, then ultrasonically cleaned with absolute alcohol and acetone for 10 min to eliminate organic matter, and finally N-washed₂Drying for later use;

(2) preparing a super-hydrophobic structure by electrodeposition:

the electrolyte formula comprises sulfonated modified graphene oxide, linolenic acid, benzotriazole and absolute ethyl alcohol, and the mass fractions of the electrolyte formula are respectively as follows: 20-30% of sulfonated modified graphene oxide, 10-20% of linolenic acid, 5-10% of benzotriazole and 40-70% of absolute ethyl alcohol, wherein the sum of the percentage contents of all the components is 100%. The sulfonated modified graphene oxide was purchased from Suzhou high-pass New Material science and technology Co. The preparation method of the sulfonated modified graphene oxide-based super-hydrophobic B30 copper-nickel alloy surface provided by the invention has the advantages that the constant potential is 1-5V, the electrodeposition time is 5-10 h, and the temperature is 30-50 ℃. On one hand, the invention utilizes linolenic acid to etch B30 copper-nickel alloy; on the other hand, a chelate is formed by benzotriazole and copper, and meanwhile, a film with high blocking performance is formed on the surface of the B30 copper-nickel alloy by utilizing the strong adsorption force of the sulfonated modified graphene oxide, so that a super-hydrophobic surface is constructed, and the super-hydrophobic B30 copper-nickel alloy has excellent corrosion resistance. The preparation process is simple, the reproducibility is good, expensive equipment is not needed, and the method has wide industrial application prospect.

The invention has the beneficial effects that:

1. the invention provides a preparation method of a sulfonated modified graphene oxide-based super-hydrophobic B30 copper-nickel alloy surface, which can obviously improve the corrosion resistance of the sulfonated modified graphene oxide-based super-hydrophobic B30 copper-nickel alloy surface in a seawater corrosion medium;

2. the invention provides a preparation method of a sulfonated modified graphene oxide-based super-hydrophobic B30 copper-nickel alloy surface, wherein linolenic acid and sulfonated modified graphene oxide are adopted as electrolyte, and the obtained film layer has better super-hydrophobic performance;

3. the invention provides a preparation method of a sulfonated modified graphene oxide-based super-hydrophobic B30 copper-nickel alloy surface, which has lower applied voltage and can effectively reduce energy consumption;

4. the invention provides a preparation method of a sulfonated modified graphene oxide-based super-hydrophobic B30 copper-nickel alloy surface, wherein the electrodeposition time is short, and the super-hydrophobic surface can be constructed in only 5 hours at a voltage of 5V;

5. the invention provides a preparation method of a sulfonated modified graphene oxide-based super-hydrophobic B30 copper-nickel alloy surface, and the super-hydrophobic film has longer service life;

6. the invention provides a preparation method of a sulfonated modified graphene oxide-based super-hydrophobic B30 copper-nickel alloy surface, which has a super-hydrophobic structure, excellent corrosion resistance and excellent protection effect on B30 copper-nickel alloy in a seawater corrosion medium;

7. the invention provides a preparation method of a sulfonated modified graphene oxide-based super-hydrophobic B30 copper-nickel alloy surface, wherein the preparation method is simple, the energy consumption is low, and an electrolyte formula is non-toxic and pollution-free and can be applied to large-scale industrial application.

Drawings

FIG. 1: contact angle of untreated B30 cupronickel;

FIG. 2: the contact angle of the surface of the sulfonated modified graphene oxide-based super-hydrophobic B30 copper-nickel alloy is shown;

FIG. 3: the electrochemical impedance result of the untreated B30 copper-nickel alloy in a simulated seawater corrosion medium (the detection result of the sea water in the east China sea is that distilled water +2.5 percent NaCl +0.2 percent CaCl2+0.6 percent MgCl2.6H20+0.5 percent Na2SO4+0.15 percent NaHC03+0.08 percent KCl);

FIG. 4: electrochemical impedance results of the sulfonated modified graphene oxide-based super-hydrophobic B30 copper-nickel alloy in simulated seawater corrosion media (east China sea water detection results: distilled water + 2.5% NaCl + 0.2% CaCl2+ 0.6% MgCl2.6H20+ 0.5% Na2SO4+ 0.15% NaHC03+ 0.08% KCl).

Detailed Description

The invention is further described below with reference to the figures and examples. While the invention will be described in conjunction with the preferred embodiments, it will be understood that they are not intended to limit the invention to the embodiments. On the contrary, the invention is intended to cover alternatives, modifications and equivalents, which may be included within the scope of the invention as defined by the appended claims.

Example 1:

(1) b30 copper-nickel alloy pretreatment:

(2) preparing a super-hydrophobic structure by electrodeposition:

the electrolyte formula comprises sulfonated modified graphene oxide, linolenic acid, benzotriazole and absolute ethyl alcohol, and the mass fractions of the electrolyte formula are respectively as follows: 20% of sulfonated modified graphene oxide, 10% of linolenic acid, 5% of benzotriazole and 65% of absolute ethyl alcohol. The preparation method of the super-hydrophobic B30 copper-nickel alloy surface provided by the invention has the advantages that the constant potential is 5V, the electrodeposition time is 5 h, and the temperature is 30 ℃.

The contact angle of the prepared sulfonated modified graphene oxide-based super-hydrophobic B30 copper-nickel alloy surface is measured by a contact angle tester, and compared with that of B30 copper-nickel alloy which is not subjected to super-hydrophobic treatment, the result is shown in figures 1 and 2, and after the treatment by the method, the contact angle of the B30 copper-nickel alloy is higher than 150 degrees.

Example 2:

(1) b30 copper-nickel alloy pretreatment:

(2) preparing a super-hydrophobic structure by electrodeposition:

the electrolyte formula comprises sulfonated modified graphene oxide, linolenic acid, benzotriazole and absolute ethyl alcohol, and the mass fractions of the electrolyte formula are respectively as follows: 30% of sulfonated modified graphene oxide, 20% of linolenic acid, 10% of benzotriazole and 40% of absolute ethyl alcohol. The preparation method of the super-hydrophobic B30 copper-nickel alloy surface provided by the invention has the advantages that the constant potential is 1V, the electrodeposition time is 10 h, and the temperature is 50 ℃.

The electrochemical impedance test of the lithium sulfonate modified graphene oxide-based super-hydrophobic B30 copper-nickel alloy is carried out in a simulated seawater corrosion medium (the detection result of east sea seawater is that distilled water is + 2.5% NaCl + 0.2% CaCl2+ 0.6% MgCl2.6H20+ 0.5% Na2SO4+ 0.15% NaHC03+ 0.08% KCl), and compared with the B30 copper-nickel alloy which is not subjected to super-hydrophobic treatment, the results are shown in a figure 3, a figure 4 and a table 2, after the treatment by the method, the membrane resistance and the charge transfer resistance are obviously increased, and the prepared sulfonated modified graphene oxide-based super-hydrophobic B30 copper-nickel alloy has better corrosion resistance.

TABLE 2

Condition	R_f, Ω.cm²	R_ct, Ω.cm²	Corrosion inhibition efficiency%
				Without super-hydrophobic treatment	652	764
Super-hydrophobic	18926	38152	97.5%

Claims

1. A preparation method of a sulfonated modified graphene oxide-based super-hydrophobic B30 copper-nickel alloy surface is characterized by comprising the following two steps:

(1) b30 copper-nickel alloy pretreatment:

(2) preparing a super-hydrophobic structure by electrodeposition:

the electrolyte formula comprises sulfonated modified graphene oxide, linolenic acid, benzotriazole and absolute ethyl alcohol, and the mass fractions of the electrolyte formula are respectively as follows: 20-30% of sulfonated modified graphene oxide, 10-20% of linolenic acid, 5-10% of benzotriazole and 40-70% of absolute ethyl alcohol, wherein the sum of the percentage contents of all the components is 100%.

2. The preparation method of the graphene-based super-hydrophobic B30 copper-nickel alloy surface provided by the invention has the advantages that the constant potential is 1-5V, the electrodeposition time is 5-10 h, and the temperature is 30-50 ℃, so that the sulfonated modified graphene-based super-hydrophobic B30 copper-nickel alloy surface can be obtained, and the super-hydrophobic B30 copper-nickel alloy has excellent corrosion resistance in simulated seawater corrosion medium.

3. The method for preparing the sulfonated modified graphene oxide-based super-hydrophobic B30 copper-nickel alloy surface according to claim 1, wherein the electrolyte formula comprises sulfonated modified graphene oxide, linolenic acid, benzotriazole and absolute ethyl alcohol.

4. The method for preparing the sulfonated modified graphene oxide-based super-hydrophobic B30 CuNi alloy surface according to claim 1, wherein the sulfonated modified graphene oxide is purchased from Suzhou high-pass New materials science and technology Limited.

5. The method for preparing the sulfonated and modified graphene oxide-based super-hydrophobic B30 copper-nickel alloy surface according to claim 1, wherein the B30 copper-nickel alloy is firstly sanded by 60-mesh, 120-mesh, 320-mesh, 600-mesh and 1200-mesh sandpaper respectively to remove impurities and oxides on the surface.

6. The method for preparing the sulfonated modified graphene oxide-based super-hydrophobic B30 copper-nickel alloy surface according to claim 1, wherein the B30 copper-nickel alloy subjected to oil removal is subjected to N treatment₂And drying for later use.

7. The method for preparing the sulfonated modified graphene oxide-based super-hydrophobic B30 copper-nickel alloy surface according to claim 1, wherein the simulated seawater is distilled water + 2.5% NaCl + 0.2% CaCl2+ 0.6% MgCl2.6H20+ 0.5% Na2SO4+ 0.15% NaHC03+ 0.08% KCl.

8. The method for preparing the sulfonated modified graphene oxide-based super-hydrophobic B30 copper-nickel alloy surface according to claim 1, wherein the constant potential is 1-5V.

9. The method for preparing the sulfonated modified graphene oxide-based super-hydrophobic B30 copper-nickel alloy surface according to claim 1, wherein the electrodeposition time is 5-10 h.

10. The method for preparing the sulfonated modified graphene oxide-based super-hydrophobic B30 copper-nickel alloy surface according to claim 1, wherein the electrodeposition temperature is 30-50 ℃.