CN112064082A - Preparation method of sulfonated modified graphene oxide-based super-hydrophobic magnesium alloy surface - Google Patents
Preparation method of sulfonated modified graphene oxide-based super-hydrophobic magnesium alloy surface Download PDFInfo
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- CN112064082A CN112064082A CN201910497328.1A CN201910497328A CN112064082A CN 112064082 A CN112064082 A CN 112064082A CN 201910497328 A CN201910497328 A CN 201910497328A CN 112064082 A CN112064082 A CN 112064082A
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- magnesium alloy
- graphene oxide
- modified graphene
- hydrophobic
- sulfonated
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/42—Pretreatment of metallic surfaces to be electroplated of light metals
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 magnesium alloy surface. The invention provides a preparation method of a sulfonated modified graphene oxide-based super-hydrophobic magnesium 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 magnesium alloy is etched in a linolenic acid medium to construct a rough structure on the surface of the magnesium alloy, on the other hand, the lamellar blocking function of the sulfonated modified graphene oxide is fully exerted, the corrosion inhibition efficiency reaches more than 97 percent, and the magnesium alloy has wide industrial application prospect.
Description
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 magnesium alloy surface.
Background
The magnesium alloy has the advantages of small relative density, high specific strength, good processing, welding and damping properties, stable size, low price, recyclability and the like, and has wide application prospect in the fields of automobiles, electronics, machinery, aviation, aerospace and the like. However, the electrode potential of the magnesium alloy is very negative, the chemical property is active, and the magnesium alloy is very easy to corrode in humid atmosphere or neutral saline solution, so that the effective inhibition of the corrosion of the magnesium alloy is very necessary for the development of the application of the magnesium alloy.
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 the super-hydrophobic magnesium alloy surface, which is simple, efficient and long in service life, has important economic and social meanings.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a quick preparation method of a super-hydrophobic magnesium alloy surface with long service life, and the super-hydrophobic structure constructed by the method is stable and is particularly suitable for protecting the magnesium alloy in an HCl corrosion medium with the mass fraction of 10%.
The invention provides a preparation method of a sulfonated modified graphene oxide-based super-hydrophobic magnesium alloy surface, which comprises the following steps:
(1) magnesium alloy pretreatment:
the magnesium alloy is firstly respectively polished by 60-mesh, 120-mesh, 320-mesh, 600-mesh and 1200-mesh sandpaper to remove impurities and oxides on the surface, then ultrasonically cleaned by isopropanol and acetone for 10 minutes to remove organic matters, and finally N is added2Drying for later use;
(2) preparing a super-hydrophobic structure by electrodeposition:
the electrolyte formula consists of sulfonated modified graphene oxide, linolenic acid and isopropanol, and the mass fractions of the electrolyte are respectively as follows: 30-40% of sulfonated modified graphene oxide, 5-10% of linolenic acid and 50-70% of isopropanol, wherein the sum of the percentage contents of 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 super-hydrophobic magnesium alloy surface provided by the invention has the advantages that the constant potential is 1-5V, the electrodeposition time is 4-10 h, and the temperature is 30-50 ℃. On one hand, the invention utilizes linolenic acid to etch the magnesium alloy; on the other hand, the strong adsorption force of the sulfonated modified graphene oxide on the surface of the magnesium alloy is utilized to form a high-blocking-performance film layer to construct a super-hydrophobic surface, so that the super-hydrophobic magnesium 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 magnesium alloy surface, which can obviously improve the corrosion resistance of a magnesium alloy in an HCl corrosion medium with the mass fraction of 10%;
2. the invention provides a preparation method of a sulfonated modified graphene oxide-based super-hydrophobic magnesium 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 magnesium 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 magnesium alloy surface, wherein the electrodeposition time is short, and the super-hydrophobic surface can be constructed in only 10 hours under the voltage of 1V;
5. the invention provides a preparation method of a sulfonated modified graphene oxide-based super-hydrophobic magnesium 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 magnesium alloy surface, which has a super-hydrophobic structure, excellent corrosion resistance and excellent protection effect on a magnesium alloy in an HCl corrosion medium with the mass fraction of 10%;
7. the invention provides a preparation method of a sulfonated modified graphene oxide-based super-hydrophobic magnesium alloy surface, wherein the preparation method is simple, the energy consumption is low, and the electrolyte formula is non-toxic and pollution-free and can be applied to large-scale industrial application.
Drawings
FIG. 1: contact angle of untreated magnesium alloy;
FIG. 2: the contact angle of the surface of the sulfonated modified graphene oxide-based super-hydrophobic magnesium alloy is determined;
FIG. 3: the electrochemical impedance test result of the untreated magnesium alloy in a 3.5% NaCl solution corrosion medium;
FIG. 4: electrochemical impedance results of the sulfonated modified graphene oxide-based super-hydrophobic magnesium alloy in a 3.5% NaCl solution corrosion medium.
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:
the invention provides a preparation method of a sulfonated modified graphene oxide-based super-hydrophobic magnesium alloy surface, which comprises the following steps:
(1) magnesium alloy pretreatment:
the magnesium alloy is firstly respectively polished by 60-mesh, 120-mesh, 320-mesh, 600-mesh and 1200-mesh sandpaper to remove impurities and oxides on the surface, then ultrasonically cleaned by isopropanol and acetone for 10 minutes to remove organic matters, and finally N is added2Drying for later use;
(2) preparing a super-hydrophobic structure by electrodeposition:
the electrolyte formula consists of sulfonated modified graphene oxide, linolenic acid and isopropanol, and the mass fractions of the electrolyte are respectively as follows: 30% of sulfonated modified graphene oxide, 5% of linolenic acid and 65% of isopropanol. The preparation method of the super-hydrophobic magnesium alloy surface provided by the invention has the advantages that the constant potential is 5V, the electrodeposition time is 4 h, and the temperature is 50 ℃.
The contact angle of the prepared sulfonated modified graphene oxide-based super-hydrophobic magnesium alloy surface is measured by a contact angle tester, and compared with the magnesium alloy without super-hydrophobic treatment, the result is shown in fig. 1 and 2, and after the magnesium alloy surface is treated by the method, the contact angle of the magnesium alloy is higher than 150 degrees.
Example 2:
the invention provides a preparation method of a graphene-based super-hydrophobic magnesium alloy surface, which comprises the following steps:
(1) magnesium alloy pretreatment:
the magnesium alloy is firstly respectively polished by 60-mesh, 120-mesh, 320-mesh, 600-mesh and 1200-mesh sandpaper to remove impurities and oxides on the surface, then ultrasonically cleaned by isopropanol and acetone for 10 minutes to remove organic matters, and finally N is added2Drying for later use;
(2) preparing a super-hydrophobic structure by electrodeposition:
the electrolyte formula consists of sulfonated modified graphene oxide, linolenic acid and isopropanol, and the mass fractions of the electrolyte are respectively as follows: 40% of sulfonated modified graphene oxide, 10% of linolenic acid and 50% of isopropanol. The preparation method of the super-hydrophobic magnesium 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 40 ℃.
Electrochemical impedance test is carried out on the sulfonated modified graphene oxide-based super-hydrophobic magnesium alloy in an HCl corrosion medium with the mass fraction of 10%, and compared with magnesium alloy which is not subjected to super-hydrophobic treatment, the result is shown in fig. 3, fig. 4 and table 2.
TABLE 2
Condition | Rct, Ω.cm2 | Corrosion inhibition efficiency% |
Without super-hydrophobic treatment | 12.6 | |
Super-hydrophobic | 562 | 97.8% |
Claims (9)
1. A preparation method of a sulfonated modified graphene oxide-based super-hydrophobic magnesium alloy surface is characterized by comprising the following two steps:
(1) magnesium alloy pretreatment:
the magnesium alloy is firstly respectively polished by 60-mesh, 120-mesh, 320-mesh, 600-mesh and 1200-mesh sandpaper to remove impurities and oxides on the surface, then ultrasonically cleaned by isopropanol and acetone for 10 minutes to remove organic matters, and finally N is added2Drying for later use;
(2) preparing a super-hydrophobic structure by electrodeposition:
the electrolyte formula comprises sulfonated modified graphene oxide, linolenic acid and isopropanol, and the mass fractions are respectively as follows: 30-40% of sulfonated modified graphene oxide, 5-10% of linolenic acid and 50-70% of isopropanol, wherein the sum of the percentage contents of the components is 100%.
2. The preparation method of the sulfonated modified graphene oxide-based super-hydrophobic magnesium alloy surface provided by the invention has the advantages that the constant potential is 1-5V, the electrodeposition time is 4-10 h, and the temperature is 30-50 ℃, so that the sulfonated modified graphene oxide-based super-hydrophobic magnesium alloy surface can be obtained, and the super-hydrophobic magnesium alloy has excellent corrosion resistance in an HCl corrosion medium with the mass fraction of 10%.
3. The method for preparing the sulfonated modified graphene oxide-based super-hydrophobic magnesium alloy surface according to claim 1, wherein the electrolyte formula consists of sulfonated modified graphene oxide, linolenic acid and isopropanol.
4. The method for preparing the sulfonated modified graphene oxide-based super-hydrophobic magnesium alloy surface according to claim 1, wherein the sulfonated modified graphene oxide is purchased from Suzhou high-pass New Material science and technology, Inc.
5. The method for preparing the sulfonated and modified graphene oxide-based super-hydrophobic magnesium alloy surface according to claim 1, wherein the magnesium 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 and modified graphene oxide-based super-hydrophobic magnesium alloy surface according to claim 1, wherein the magnesium alloy subjected to oil removal is subjected to N treatment2And drying for later use.
7. The method for preparing the sulfonated and modified graphene oxide-based super-hydrophobic magnesium alloy surface according to claim 1, wherein the constant potential is 1-5V.
8. The method for preparing the sulfonated modified graphene oxide-based super-hydrophobic magnesium alloy surface according to claim 1, wherein the electrodeposition time is 4-10 h.
9. The method for preparing the sulfonated and modified graphene oxide-based super-hydrophobic magnesium alloy surface according to claim 1, wherein the electrodeposition temperature is 30-50 ℃.
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