CN110629266B - Preparation method of super-hydrophobic stainless steel surface with self-repairing characteristic - Google Patents

Preparation method of super-hydrophobic stainless steel surface with self-repairing characteristic Download PDF

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CN110629266B
CN110629266B CN201911047949.6A CN201911047949A CN110629266B CN 110629266 B CN110629266 B CN 110629266B CN 201911047949 A CN201911047949 A CN 201911047949A CN 110629266 B CN110629266 B CN 110629266B
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杨洋
陈宇
杨吟野
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Chongqing Juyuan Stainless Steel Products Co ltd
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    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C25D5/36Pretreatment of metallic surfaces to be electroplated of iron or steel
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Abstract

The invention belongs to the technical field of functional materials, and relates to a preparation method of a super-hydrophobic stainless steel surface with a self-repairing characteristic. The invention provides a preparation method of a super-hydrophobic stainless steel surface with self-repairing characteristic, which comprises the following steps: the super-hydrophobic structure is prepared by adopting an electrodeposition method. On one hand, the stainless steel is etched by utilizing linolenic acid; on the other hand, a high-barrier-performance film layer is formed by utilizing the strong adsorption force of the modified graphene oxide on the surface of the stainless steel, so that a super-hydrophobic surface is constructed; meanwhile, the cerium dioxide self-repairing film is obtained by deposition on the surface of the stainless steel, so that the super-hydrophobic stainless steel has excellent and lasting corrosion resistance, the corrosion inhibition efficiency reaches more than 97 percent, and the method has a wide industrial application prospect.

Description

Preparation method of super-hydrophobic stainless steel surface with self-repairing characteristic
Technical Field
The invention belongs to the technical field of functional materials, and particularly relates to a preparation method of a super-hydrophobic stainless steel surface with a self-repairing characteristic.
Background
Stainless steel is a general metal material, and has good corrosion resistance, heat resistance, low-temperature strength and mechanical properties, good hot workability such as stamping and bending, and no hot treatment hardening phenomenon, so that the stainless steel is widely applied to the fields of chemical industry, electric power, navigation, weaponry and the like to manufacture machines and parts such as heat exchange equipment, containers, valves, pumps, turbines, shafts and the like. However, when exposed to corrosive media, particularly chloride ion-containing environments, severe corrosion can occur.
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.
On the other hand, CeO2Due to the outstanding chemical stability, corrosion resistance and self-repairing property, the Cr (VI) conversion film is a main substitute of a high-toxicity Cr (VI) conversion film with excellent corrosion resistance recognized at home and abroad, and has potential wide application prospect in the field of protection of metal materials.
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 of the simple, high-efficiency and long-life super-hydrophobic stainless steel has important economic significance and social significance.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a method for preparing a quick and long-life super-hydrophobic stainless steel, and the super-hydrophobic structure constructed by the method is stable and is particularly suitable for protecting 304 stainless steel in a 3.5% NaCl solution corrosion medium.
The invention provides a preparation method of a super-hydrophobic stainless steel surface with self-repairing characteristic, which comprises the following three steps:
firstly, stainless steel pretreatment:
the stainless steel is firstly polished by 60-mesh, 120-mesh, 320-mesh, 600-mesh and 1200-mesh sandpaper respectively to remove impurities and oxides on the surface, then ultrasonically cleaned by absolute ethyl alcohol and acetone for 10 minutes to remove organic matters, and finally subjected to N treatment2Drying for later use;
step two, preparing electrolyte:
respectively taking 3 beakers with the volume of 100 mL, and dissolving cerium nitrate in deionized water in one beaker; dissolving linolenic acid in absolute ethyl alcohol in a second beaker; dissolving the alkylated modified graphene oxide in deionized water in a third beaker, performing ultrasonic dispersion for 1 hour until the solution is uniform and transparent, then mixing the liquids in the three beakers, magnetically stirring for half hour, and performing ultrasonic dispersion for 2 hours until the mixed solution is uniform and transparent;
thirdly, preparing a super-hydrophobic structure by electrodeposition:
and (2) performing constant-voltage electrodeposition by adopting a ZF-9 potentiostat, soaking the treated stainless steel serving as a working electrode in the electrolyte, taking a large-area platinum sheet as an auxiliary electrode and a saturated calomel electrode as a reference electrode, setting the electrodeposition voltage value to be 5-20V and the electrodeposition time to be 4-12h, putting the electrodeposition device into a constant-temperature water bath kettle in the electrodeposition process, and setting the temperature to be 30-50 ℃ to obtain the super-hydrophobic stainless steel surface with the self-repairing characteristic.
Preferably, the mass fractions of the chemical substances in the mixed solution are respectively: 10-20% of alkylated modified graphene oxide, 20-30% of linolenic acid, 5-10% of cerium nitrate, 20-40% of absolute ethyl alcohol and 20-30% of deionized water, wherein the sum of the percentage contents of all the components is 100%.
In any of the above embodiments, preferably, the linolenic acid and the cerium nitrate are both analytical reagents.
The invention has the following advantages:
1. the invention provides a preparation method of a super-hydrophobic stainless steel surface with self-repairing characteristics, which can obviously improve the corrosion resistance of 304 stainless steel in a 3.5% NaCl solution corrosion medium;
2. the invention provides a preparation method of a super-hydrophobic stainless steel surface with self-repairing characteristics, wherein linolenic acid and alkylated 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 super-hydrophobic stainless steel surface with self-repairing characteristics, applied voltage is low, and energy consumption can be effectively reduced;
4. the invention provides a preparation method of a super-hydrophobic stainless steel surface with self-repairing characteristics, wherein the electro-deposition time is short, and the super-hydrophobic surface can be constructed in only 6 hours under the voltage of 10V;
5. the invention provides a preparation method of a super-hydrophobic stainless steel surface with self-repairing characteristics, wherein the formation of a cerium dioxide self-repairing film enables the service life of the super-hydrophobic film to be longer;
6. the invention provides a preparation method of a super-hydrophobic stainless steel surface with self-repairing characteristics, which not only has a super-hydrophobic structure, but also has excellent corrosion resistance, and has excellent protection effect on 304 stainless steel in a 3.5% NaCl solution corrosion medium;
7. the invention provides a preparation method of a super-hydrophobic stainless steel surface with self-repairing characteristics, wherein the preparation method is simple, the energy consumption is low, the electrolyte formula is non-toxic and pollution-free, and the preparation method can be applied to large-scale industrial application.
Drawings
Fig. 1 is a contact angle of untreated 304 stainless steel.
Fig. 2 is a contact angle of superhydrophobic-modified 304 stainless steel.
FIG. 3 shows the polarization curve test results of the treated 304 stainless steel in a 3.5% NaCl solution corrosion medium.
FIG. 4 shows the results of a curve test of the superhydrophobic-modified 304 stainless steel in a 3.5% NaCl solution corrosive medium.
FIG. 5 shows the polarization curve test results of untreated 304 stainless steel in a 3.5% NaCl solution corrosion medium.
FIG. 6 shows the polarization curve test results of the superhydrophobic-modified 304 stainless steel in a 3.5% NaCl solution corrosion medium.
Detailed Description
The following description is merely exemplary in nature and is not intended to limit the present disclosure, application, or uses. The following description will further describe a specific embodiment of the method for preparing the super-hydrophobic stainless steel surface with self-repairing property according to the present invention with reference to the attached drawings.
Example 1:
the invention provides a preparation method of a super-hydrophobic stainless steel surface with self-repairing characteristic, which comprises the following steps:
firstly, stainless steel pretreatment:
the stainless steel is firstly polished by 60-mesh, 120-mesh, 320-mesh, 600-mesh and 1200-mesh sandpaper respectively to remove impurities and oxides on the surface, then ultrasonically cleaned by absolute ethyl alcohol and acetone for 10 minutes to remove organic matters, and finally subjected to N treatment2Drying for later use;
step two, preparing electrolyte:
respectively taking 3 beakers with the volume of 100 mL, and dissolving cerium nitrate in deionized water in one beaker; dissolving linolenic acid in absolute ethyl alcohol in a second beaker; dissolving the alkylated modified graphene oxide in deionized water in a third beaker, performing ultrasonic dispersion for 1 hour until the solution is uniform and transparent, then mixing the liquids in the three beakers, magnetically stirring for half hour, and performing ultrasonic dispersion for 2 hours until the mixed solution is uniform and transparent;
thirdly, preparing a super-hydrophobic structure by electrodeposition:
and (2) performing constant-voltage electrodeposition by adopting a ZF-9 potentiostat, soaking the treated stainless steel serving as a working electrode in the electrolyte, taking a large-area platinum sheet as an auxiliary electrode and a saturated calomel electrode as a reference electrode, setting the electrodeposition voltage value to be 5V and the electrodeposition time to be 12h, putting the electrodeposition device into a constant-temperature water bath kettle in the electrodeposition process, and setting the temperature to be 50 ℃ to obtain the super-hydrophobic stainless steel surface with the self-repairing characteristic.
The electrolyte formula comprises alkylated modified graphene oxide, linolenic acid, cerium nitrate, absolute ethyl alcohol and deionized water, and the mass fractions are respectively as follows: 10% of alkylated modified graphene oxide, 20% of linolenic acid, 10% of cerium nitrate, 40% of absolute ethyl alcohol and 20% of deionized water.
The contact angle of the prepared super-hydrophobic modified stainless steel is measured by a contact angle tester, and compared with the contact angle of the stainless steel which is not subjected to super-hydrophobic treatment, the contact angle of the stainless steel treated by the method is higher than 150 degrees, and the results are shown in figures 1 and 2.
Example 2:
the invention provides a preparation method of a super-hydrophobic stainless steel surface with self-repairing characteristic, which comprises the following steps:
firstly, stainless steel pretreatment:
the stainless steel is firstly polished by 60-mesh, 120-mesh, 320-mesh, 600-mesh and 1200-mesh sandpaper respectively to remove impurities and oxides on the surface, then ultrasonically cleaned by absolute ethyl alcohol and acetone for 10 minutes to remove organic matters, and finally subjected to N treatment2Drying for later use;
step two, preparing electrolyte:
respectively taking 3 beakers with the volume of 100 mL, and dissolving cerium nitrate in deionized water in one beaker; dissolving linolenic acid in absolute ethyl alcohol in a second beaker; dissolving the alkylated modified graphene oxide in deionized water in a third beaker, performing ultrasonic dispersion for 1 hour until the solution is uniform and transparent, then mixing the liquids in the three beakers, magnetically stirring for half hour, and performing ultrasonic dispersion for 2 hours until the mixed solution is uniform and transparent;
thirdly, preparing a super-hydrophobic structure by electrodeposition:
and (2) performing constant-voltage electrodeposition by adopting a ZF-9 potentiostat, soaking the treated stainless steel serving as a working electrode in the electrolyte, taking a large-area platinum sheet as an auxiliary electrode and a saturated calomel electrode as a reference electrode, setting the electrodeposition voltage value to be 20V and the electrodeposition time to be 6h, putting the electrodeposition device into a constant-temperature water bath kettle in the electrodeposition process, and setting the temperature to be 30 ℃ to obtain the super-hydrophobic stainless steel surface with the self-repairing characteristic.
The electrolyte formula comprises alkylated modified graphene oxide, linolenic acid, cerium nitrate, absolute ethyl alcohol and deionized water, and the mass fractions are respectively as follows: 20% of alkylated modified graphene oxide, 30% of linolenic acid, 5% of cerium nitrate, 20% of absolute ethyl alcohol and 25% of deionized water.
Electrochemical impedance test is carried out on the super-hydrophobic modified stainless steel in a 3.5% NaCl solution corrosion medium, and compared with 304 stainless steel which is not subjected to super-hydrophobic treatment, the results are shown in fig. 3 and fig. 4 and table 1, after the super-hydrophobic modified stainless steel is treated by the method, the charge transfer resistance is obviously increased, and the prepared super-hydrophobic modified stainless steel has better corrosion resistance.
TABLE 1
Figure DEST_PATH_IMAGE001
Example 3:
the invention provides a preparation method of a super-hydrophobic stainless steel surface with self-repairing characteristic, which comprises the following steps:
firstly, stainless steel pretreatment:
the stainless steel is firstly polished by 60-mesh, 120-mesh, 320-mesh, 600-mesh and 1200-mesh sandpaper respectively to remove impurities and oxides on the surface, and then is ultrasonically cleaned by absolute ethyl alcohol and acetone for 10 minutes to remove organic mattersIs then passed over N2Drying for later use;
step two, preparing electrolyte:
respectively taking 3 beakers with the volume of 100 mL, and dissolving cerium nitrate in deionized water in one beaker; dissolving linolenic acid in absolute ethyl alcohol in a second beaker; dissolving the alkylated modified graphene oxide in deionized water in a third beaker, performing ultrasonic dispersion for 1 hour until the solution is uniform and transparent, then mixing the liquids in the three beakers, magnetically stirring for half hour, and performing ultrasonic dispersion for 2 hours until the mixed solution is uniform and transparent;
thirdly, preparing a super-hydrophobic structure by electrodeposition:
and (2) performing constant-voltage electrodeposition by adopting a ZF-9 potentiostat, soaking the treated stainless steel serving as a working electrode in the electrolyte, taking a large-area platinum sheet as an auxiliary electrode and a saturated calomel electrode as a reference electrode, setting the electrodeposition voltage value to be 10V and the electrodeposition time to be 4 h, putting the electrodeposition device into a constant-temperature water bath kettle in the electrodeposition process, and setting the temperature to be 40 ℃ to obtain the super-hydrophobic stainless steel surface with the self-repairing characteristic.
The electrolyte formula comprises alkylated modified graphene oxide, linolenic acid, cerium nitrate, absolute ethyl alcohol and deionized water, and the mass fractions are respectively as follows: 15% of alkylated modified graphene oxide, 20% of linolenic acid, 5% of cerium nitrate, 30% of absolute ethyl alcohol and 30% of deionized water.
The super-hydrophobic modified stainless steel is subjected to a polarization curve test in a 3.5% NaCl solution corrosion medium, and compared with the 304 stainless steel which is not subjected to super-hydrophobic treatment, the results are shown in fig. 5, fig. 6 and table 2, and the self-corrosion current is obviously reduced after the treatment by the method, which indicates that the prepared super-hydrophobic modified stainless steel has better corrosion resistance.
TABLE 2
Figure DEST_PATH_IMAGE002

Claims (2)

1. A preparation method of a super-hydrophobic stainless steel surface with self-repairing characteristics is characterized by comprising the following steps: the preparation method comprises the following three steps:
firstly, stainless steel pretreatment:
the stainless steel is firstly polished by 60-mesh, 120-mesh, 320-mesh, 600-mesh and 1200-mesh sandpaper respectively to remove impurities and oxides on the surface, then ultrasonically cleaned by absolute ethyl alcohol and acetone for 10 minutes to remove organic matters, and finally subjected to N treatment2Drying for later use;
step two, preparing electrolyte:
respectively taking 3 beakers with the volume of 100 mL, and dissolving cerium nitrate in deionized water in one beaker; dissolving linolenic acid in absolute ethyl alcohol in a second beaker; dissolving the alkylated modified graphene oxide in deionized water in a third beaker, performing ultrasonic dispersion for 1 hour until the solution is uniform and transparent, then mixing the liquids in the three beakers, magnetically stirring for half hour, and performing ultrasonic dispersion for 2 hours until the mixed solution is uniform and transparent;
the mass fractions of all chemical substances in the mixed solution are respectively as follows: 10-20% of alkylated modified graphene oxide, 20-30% of linolenic acid, 5-10% of cerium nitrate, 20-40% of absolute ethyl alcohol and 20-30% of deionized water, wherein the sum of the percentage contents of all the components is 100%;
thirdly, preparing a super-hydrophobic structure by electrodeposition:
and (2) performing constant-voltage electrodeposition by adopting a ZF-9 potentiostat, soaking the treated stainless steel serving as a working electrode in the electrolyte, taking a large-area platinum sheet as an auxiliary electrode and a saturated calomel electrode as a reference electrode, setting the electrodeposition voltage value to be 5-20V and the electrodeposition time to be 4-12h, putting the electrodeposition device into a constant-temperature water bath kettle in the electrodeposition process, and setting the temperature to be 30-50 ℃ to obtain the super-hydrophobic stainless steel surface with the self-repairing characteristic.
2. The method for preparing the super-hydrophobic stainless steel surface with the self-repairing property as claimed in claim 1, wherein the method comprises the following steps: the linolenic acid and the cerium nitrate are analytical pure chemical reagents.
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