CN113564573B - Preparation method and application of SLIPS/LDHs composite film on magnesium alloy surface - Google Patents

Preparation method and application of SLIPS/LDHs composite film on magnesium alloy surface Download PDF

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CN113564573B
CN113564573B CN202110834632.8A CN202110834632A CN113564573B CN 113564573 B CN113564573 B CN 113564573B CN 202110834632 A CN202110834632 A CN 202110834632A CN 113564573 B CN113564573 B CN 113564573B
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magnesium alloy
ldhs
composite film
slips
corrosion
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CN113564573A (en
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姚文辉
陈勇花
吴量
潘复生
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Chongqing University
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
    • C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
    • C23C22/60—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using alkaline aqueous solutions with pH greater than 8
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
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    • C23C22/83—Chemical after-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D2202/00—Metallic substrate
    • B05D2202/20—Metallic substrate based on light metals
    • C—CHEMISTRY; METALLURGY
    • C23—COATING 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
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2222/00—Aspects relating to chemical surface treatment of metallic material by reaction of the surface with a reactive medium
    • C23C2222/20—Use of solutions containing silanes

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Abstract

The invention relates to a preparation method of a SLIPS/LDHs composite film on the surface of a magnesium alloy, which comprises the steps of firstly growing a ternary MgAlLa-LDHs film on a magnesium alloy substrate in situ, further utilizing the unique ion exchange performance of the LDHs to load anion benzoate, and then adopting fluorine-containing silane to carry out low surface energy modification on the LDHs, so as to realize the pouring of simethicone on the surface of the LDHs composite film, and prepare the SLIPS/LDHs composite film. The good hydrophobicity of the composite film layer can effectively isolate corrosion of external corrosive ions to the magnesium alloy matrix. The lubricating liquid with corrosion inhibition effect, namely La ions, benzoate ions and physical flow effect, can be designed on the surface of magnesium alloy in a triple self-repairing integrated manner. The preparation method is simple and low in cost, and the industrial practicability and efficiency are greatly improved. And the composite film layer can obviously improve the corrosion resistance of the magnesium alloy matrix, thereby promoting the wide application of the magnesium alloy in the fields of aerospace, automobiles, electronics and the like.

Description

Preparation method and application of SLIPS/LDHs composite film on magnesium alloy surface
Technical Field
The invention belongs to the technical field of metal surface treatment, and relates to a preparation method and application of a magnesium alloy surface SLIPS/LDHs composite film.
Background
As the lightest metal structural material in the current engineering application, the magnesium alloy has the excellent performances of low density (about 2/3 of aluminum, 1/4 of iron and 1/3 of titanium), good damping, good heat conductivity, high specific stiffness and specific strength, easy cutting processing, higher recycling rate, abundant reserves, electromagnetic interference resistance and the like, and has great application prospect and practical value in the fields of aerospace, automobile industry, medical appliances, electronic communication and the like. However, magnesium has high chemical activity and low electrode potential, so that the corrosion resistance of the magnesium is poor, and the wide application of the magnesium in practice is seriously affected. Therefore, the improvement of the corrosion resistance of the magnesium alloy to expand the application field of the magnesium alloy is an important point of research students at home and abroad.
At present, the corrosion resistance of magnesium alloys can be improved by high purification, alloying and surface treatment. The high purification is to reduce the content of harmful elements and impurities as much as possible in the alloy smelting process so as to reduce the number of easy-to-corrode phases; alloying is to add alloy elements capable of improving microstructure and structure of magnesium alloy in the smelting process so as to improve corrosion resistance; the surface treatment is to prepare a film layer on the surface of the magnesium alloy, so that the direct contact between a matrix and a corrosive medium is avoided, and the corrosion is reduced. Among them, surface treatment is widely focused by researchers because of its strong operability, numerous methods, and strong functionality. The magnesium alloy coating prepared at present still has the key problems of poor mechanical durability, weak matrix adhesion, low capability of resisting severe environment and the like.
The corrosion resistance of the magnesium alloy can be improved by controlling the structural change through heat treatment. In addition, the defects of complex operation and high cost existing in the surface treatment and other processes also bring great problems to the treatment of the magnesium alloy. There is therefore an effort to explore processes with simpler, lower cost, lower pollution characteristics.
Disclosure of Invention
The invention aims to solve the technical problem of providing a simple preparation method of a magnesium alloy surface SLIPS/LDHs composite film which is easy for industrial production and can realize triple self-repair.
In order to solve the problems, the preparation method of the SLIPS/LDHs composite film layer on the magnesium alloy surface comprises the steps of growing an MgAlLa-LDHs film layer on the magnesium alloy surface in situ; carrying out loading of corrosion inhibitor benzoate ions by virtue of unique ion exchange performance of LDHs; performing low surface energy treatment on the LDHs film layer by using fluorine-containing silane to obtain a fluorinated layer; so that the lubricating liquid is stabilized between MgAlLa-LDHs nanometer layers by virtue of the fluoride layer, thereby forming an outermost lubricating liquid layer.
1. A preparation method of a magnesium alloy surface SLIPS/LDHs composite film layer comprises the following specific steps:
a. firstly, growing a MgAlLa-LDHs film layer on the surface of the magnesium alloy in situ: immersing the cleaned magnesium alloy matrix into in-situ growth liquid, carrying out hydrothermal reaction for 12-16 hours at 110-130 ℃, taking out and washing with deionized water for multiple times to obtain magnesium alloy growing with MgAlLa-LDHs film layers; according to the mass concentration of the substances, the in-situ growth liquid is an aqueous solution of 0.02-0.1M of aluminum nitrate, 0.05-0.25M of sodium nitrate and 0.001-0.025M of lanthanum nitrate, and the pH value is 9.5-12;
b. then immersing the magnesium alloy into 0.1M-0.5M sodium benzoate solution, reacting for 2-4 hours at 50-70 ℃;
c. fluorinated layer: immersing the magnesium alloy treated in the step b into anhydrous ethanol solution containing fluorine silane, carrying out fluorination treatment for 2-4 hours, cleaning and drying to obtain a fluorinated layer;
d. lubricating liquid layer: and c, dripping the lubricating liquid on the surface of the magnesium alloy treated by the step c, and then obliquely placing the magnesium alloy at an angle of 10-20 degrees to enable the lubricating liquid to flow out of the surface of the magnesium alloy to form a lubricating liquid layer, so that the magnesium alloy with the SLIPS/LDHs composite film layer is finally obtained.
Further, according to the mass concentration, the in-situ growth liquid is an aqueous solution of 0.05M of aluminum nitrate, 0.1M of sodium nitrate and 0.001M-0.025M of lanthanum nitrate, and the pH value is 9.5-12.
Further, the pH of the in-situ growth liquid in the step a is 10.8-11.2.
Further, the loading of sodium benzoate in step b was performed in deionized water solution.
Further, the concentration of the fluorine-containing silane is 0.02M to 0.05M.
Further, the fluorine-containing silane is perfluorodecyl triethoxysilane or perfluorodecyl trimethoxysilane.
Further, the lubricating fluid is selected from one or more of simethicone, krytox lubricating oil and perfluoropolyether;
the Krytox lubricating oil is a Krytox series lubricating oil produced by DuPont.
Further, in the step a, the surface of the magnesium alloy is cleaned by deionized water; or the surface of the magnesium alloy is firstly subjected to water grinding, degreasing and degreasing, and then is cleaned by deionized water.
2. The invention provides an application of any preparation method of a SLIPS/LDHs composite film layer on the surface of a magnesium alloy in the surface treatment of the magnesium alloy.
The preparation method of the triple self-repairing SLIPS/LDHs composite film layer is applicable to various solid matrixes except magnesium alloy, such as aluminum alloy, titanium alloy, steel and the like, and has good universality.
The triple self-repairing SLIPS/LDHs composite film layer obtained by the preparation method has excellent self-cleaning performance and pollution-preventing performance: when the inclination angle is 10-15 degrees, the pollutants on the surface of the magnesium alloy slide along with water drops (5-50 mu L) to be cleaned, and no trace of the water drops or the pollutants is left.
3. The application of the product obtained by the preparation method of any magnesium alloy surface SLIPS/LDHs composite film layer provided by the invention in the fields of aerospace, automobiles, electronic products and the like also belongs to the protection scope of the invention.
The invention has the beneficial effects that: the preparation method of the SLIPS/LDHs composite film on the magnesium alloy surface is simple and effective, can realize the integrated design of triple self-repairing composite film on the magnesium alloy surface, simultaneously gives the advantages of passive isolation, active protection, intelligent self-repairing and the like to the magnesium alloy, and can further promote the wide application of the magnesium alloy in the fields of aerospace, automobiles, electronics and the like. The film layer is prepared by an in-situ growth method, and the prepared film layer is firmly combined with the magnesium alloy matrix; mgAlLa-LDHs not only provides a nano container for the filling of lubricating liquid, but also can load anionic corrosion inhibitor benzoate ions and cationic corrosion inhibitor La ions simultaneously; the pouring of SLIPS lubricating liquid can effectively seal holes on LDHs film layers, prevent corrosion of external corrosive ions to magnesium alloy, and the physical fluidity of the LDHs film layers can give the film layers self-repairing performance, so that the corrosion resistance of the magnesium alloy is effectively improved. In general, the reagent used in the whole preparation process is low in price and easy to obtain, does not pollute the environment, has simple and environment-friendly whole process, can meet the requirements of industrial development and mass production, and further expands the application range of the magnesium alloy.
Drawings
In order to make the objects, technical solutions and advantageous effects of the present invention more clear, the present invention provides the following drawings for description: in order to clearly show the technical scheme and effect of the invention, the invention provides the following drawings for explanation:
FIG. 1 is a scanning electron microscope photograph of MgAlLa-LDHs on the surface of the magnesium alloy of example 1;
FIG. 2 is a scanning electron microscope photograph of a SLIPS/LDHs composite film layer on the surface of the magnesium alloy in example 1;
FIG. 3 is a Tafil polarization curve of the AZ31 magnesium alloy, the MgAlLa-LDHs film magnesium alloy and the SLIPS/LDHs composite film magnesium alloy of example 1 under the same coordinates;
FIG. 4 is a scanning electron microscope photograph of MgAlLa-LDHs on the surface of the magnesium alloy of example 2;
FIG. 5 is a scanning electron microscope photograph of a SLIPS/LDHs composite film layer on the surface of the magnesium alloy of the embodiment 2;
FIG. 6 is Tafil polarization curves of the AZ31 magnesium alloy, the MgAlLa-LDHs film magnesium alloy and the SLIPS/LDHs composite film magnesium alloy of example 2 under the same coordinates;
FIG. 7 is a scanning electron micrograph of MgAlLa-LDHs on the surface of the magnesium alloy of example 3;
FIG. 8 is a scanning electron microscope photograph of a SLIPS/LDHs composite film layer on the surface of the magnesium alloy of the embodiment 3;
FIG. 9 is a Tafil polarization curve of the magnesium alloy of example 3AZ31, mgAlLa-LDHs film magnesium alloy and SLIPS/LDHs composite film magnesium alloy at the same coordinates;
FIG. 10 is a scanning electron micrograph of MgAlLa-LDHs on the surface of the magnesium alloy of example 4;
FIG. 11 is a scanning electron microscope photograph of a SLIPS/LDHs composite film layer on the surface of the magnesium alloy of example 4;
FIG. 12 is a Tafil polarization curve of the magnesium alloy of example 4AZ31, mgAlLa-LDHs film magnesium alloy and SLIPS/LDHs composite film magnesium alloy at the same coordinates;
FIG. 13 is a graph of water contact angle for the sample of example 1;
FIG. 14 is a graph of water contact angle for the sample of example 2;
FIG. 15 is a graph of water contact angle for a sample of example 3;
FIG. 16 is a graph of the water contact angle of example 4.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments, but the scope of the present invention is not limited to the above.
Example 1:
a preparation method of a triple self-repairing SLIPS/LDHs composite film layer on the surface of a magnesium alloy comprises the following specific steps:
1. in-situ growth of MgAlLa-LDHs film
The magnesium alloy AZ31 after water milling is soaked in the degreasing and degreasing aqueous solution (40 g/L of sodium hydroxide, 25g/L of sodium carbonate and 40g/L of sodium phosphate), the water bath is kept at 50 ℃ for 60 seconds, then is washed with 1M aqueous solution of sodium hydroxide 60 for 30 seconds, and then is polished for 1-2 minutes at room temperature of 25 ℃ by 400g/L of nitric acid (rho=1.42 g/ml). And then the mixture is washed once by deionized water and dried by cold air. (Water milling: grinding magnesium alloy matrix with 150, 600, 800, 1200, 2000# sand paper respectively, and ultrasonic cleaning with alcohol for 5 minutes, and drying for later use).
A hydrothermal reaction step: firstly, pouring electrolyte into a liner of a reaction kettle, and then placing a cleaned magnesium alloy sample into in-situ growth liquid, wherein the in-situ growth liquid is as follows: sodium nitrate 0.1M, aluminum nitrate 0.05M, lanthanum nitrate 0.001M, pH10.9; and (3) after the reaction kettle is closed, placing the reaction kettle into an electric oven for in-situ growth, wherein the reaction temperature is 125+/-5 ℃, and the constant-temperature reaction time is set to be 12 hours, so that the magnesium alloy with the ternary MgAlLa-LDHs film layer grown on the surface is obtained. The in-situ growth liquid is an aqueous solution with the concentration range of 0.02-0.1M of aluminum nitrate, 0.05-0.25M of sodium nitrate and 0.001-0.025M of lanthanum nitrate, and the pH value is 9.5-12, wherein in order to more objectively compare the parameters of other treatment methods, the embodiment only shows the effect of the in-situ growth liquid under the concentration of 0.1M of sodium nitrate, 0.05M of aluminum nitrate and 0.001M of lanthanum nitrate.
2. Supported corrosion inhibitor
And (2) immersing the magnesium alloy sample of the MgAlLa-LDHs film layer in the step (1) into a 0.1M sodium benzoate aqueous solution, wherein the water bath temperature is 60+/-5 ℃, and the constant temperature reaction time is set to be 2 hours.
3. Fluorinated layer
And (3) a fluorination treatment step: immersing the magnesium alloy sample treated in the step 2 into an absolute ethanol solution of 0.02M perfluorodecyl triethoxysilane, wherein the water bath temperature is 60+/-5 ℃, and the constant-temperature reaction time is set to be 2 hours. After the reaction is completed, the mixture is washed with water and then dried.
4. Lubricating liquid layer
And (3) adding excessive dimethyl silicon oil to the surface of the magnesium alloy sample treated in the step (3), and tilting for 1 hour at an angle of 15+/-2 degrees to enable excessive lubricating liquid to flow out of the surface of the sample, so as to finally obtain the triple self-repairing SLIPS/LDHs composite film magnesium alloy. Further detecting the structure, the morphology and the like.
FIG. 1 is a scanning electron microscope photograph of the rear surface of a MgAlLa-LDHs film layer grown on a magnesium alloy. FIG. 2 is a scanning electron microscope photograph of the surface of SLIPS/LDHs composite film magnesium alloy. FIG. 3 is Tafil polarization curves of AZ31 magnesium alloy (AZ 31), mgAlLa-LDHs film magnesium alloy (LDHs) and SLIPS/LDHs composite film magnesium alloy (SLIPS) at the same coordinates. Wherein the corrosion voltage of the pure AZ31 magnesium alloy is-1491+/-5 mV, the corrosion voltage of the MgAlLa-LDHs film magnesium alloy is-209+/-7 mV, the corrosion voltage of the triple self-repairing SLIPS/LDHs composite film AZ31 magnesium alloy prepared by the embodiment 1 is-833+/-3 mV, the corrosion voltage is improved relative to the corrosion voltage of a magnesium alloy matrix, the corrosion inclination is reduced, and the corrosion speed and the corrosion resistance are directly related to the corrosion current density. The corrosion current density of the pure AZ31 magnesium alloy is 6.7X10 -5 Acm -2 The corrosion current density of the MgAlLa-LDHs film magnesium alloy is 6.87 multiplied by 10 -7 Acm -2 The corrosion current density of SLIPS/LDHs composite film layer is 5.36×10 -9 Acm -2 The corrosion current density of the treated sample is respectively reduced by two and four orders of magnitude compared with that of a sample of the pure AZ31 magnesium alloy. The MgAlLa-LDHs film and SLIPS/LDHs composite film have effective corrosion inhibition effect on AZ31 magnesium alloy, and the SLIPS/LDHs composite film on the surface of the magnesium alloy has more excellent corrosion resistance and can more effectively protect a magnesium matrix.
Example 2
A preparation method of a triple self-repairing SLIPS/LDHs composite film layer on the surface of a magnesium alloy comprises the following specific steps:
1. in-situ growth of MgAlLa-LDHs film
The magnesium alloy AZ31 after water milling is soaked in the degreasing and degreasing aqueous solution (40 g/L of sodium hydroxide, 25g/L of sodium carbonate and 40g/L of sodium phosphate), the water bath is kept at 50 ℃ for 60 seconds, then is washed with 1M aqueous solution of sodium hydroxide 60 for 30 seconds, and then is polished for 1-2 minutes at room temperature of 25 ℃ by 400g/L of nitric acid (rho=1.42 g/ml). And then the mixture is washed once by deionized water and dried by cold air.
A hydrothermal reaction step: firstly, pouring electrolyte into a liner of a reaction kettle, and then placing a cleaned magnesium alloy sample into in-situ growth liquid, wherein the in-situ growth liquid is as follows: sodium nitrate 0.1M, aluminum nitrate 0.05M, lanthanum nitrate 0.001M, pH10.9; and (3) after the reaction kettle is closed, placing the reaction kettle into an electric oven for in-situ growth, wherein the reaction temperature is 125+/-5 ℃, and the constant-temperature reaction time is set to be 12 hours, so that the magnesium alloy with the ternary MgAlLa-LDHs film layer grown on the surface is obtained.
2. Supported corrosion inhibitor
Immersing the magnesium alloy sample in the step 1 into 0.3M sodium benzoate water solution, wherein the water bath temperature is 60+/-5 ℃, and the constant-temperature reaction time is set to be 2 hours.
3. Fluorinated layer
And (3) a fluorination treatment step: immersing the magnesium alloy sample in the step 2 into an absolute ethanol solution of 0.02M perfluorodecyl trimethoxysilane, wherein the water bath temperature is 60+/-5 ℃, and the constant-temperature reaction time is set to be 2 hours. After the reaction is completed, the mixture is washed with water and then dried.
4. Lubricating liquid layer
And (3) dropwise adding excessive perfluoropolyether to the surface of the magnesium alloy sample treated in the step (3), and inclining for 1 hour at an angle of 15+/-2 degrees to enable excessive lubricating liquid to flow out of the surface of the sample, so as to finally obtain the triple self-repairing SLIPS/LDHs composite film magnesium alloy. Further detecting the structure, the morphology and the like.
Fig. 4 is a scanning electron microscope photograph of the rear surface of the MgAlLa-LDHs film layer grown on the magnesium alloy. FIG. 5 is a scanning electron microscope photograph of the surface of SLIPS/LDHs composite film magnesium alloy. FIG. 6 is Tafil polarization curves of AZ31 magnesium alloy, mgAlLa-LDHs film magnesium alloy and SLIPS/LDHs composite film magnesium alloy at the same coordinates. The corrosion voltage of the pure AZ31 magnesium alloy is-1452+/-3 mV, the corrosion voltage of the MgAlLa-LDHs film layer is-295+/-7 mV, the corrosion voltage of the triple self-repairing SLIPS/LDHs composite film layer prepared by the embodiment 2 is-836+/-5 mV, the corrosion voltage is improved relative to the corrosion voltage of a magnesium alloy matrix, the corrosion inclination is reduced, and the corrosion speed and the corrosion resistance are directly related to the corrosion current density. The corrosion current density of the pure AZ31 magnesium alloy is 6.51X10 -5 Acm -2 The corrosion current density of the MgAlLa-LDHs film magnesium alloy is 2.46 multiplied by 10 -7 Acm -2 The corrosion current density of SLIPS/LDHs composite film layer is 5.27×10 -9 Acm -2 The corrosion current density of the treated sample is respectively reduced by two and four orders of magnitude compared with that of a sample of the pure AZ31 magnesium alloy. The MgAlLa-LDHs film and SLIPS/LDHs composite film have effective corrosion inhibition effect on AZ31 magnesium alloy, and the SLIPS/LDHs composite film on the surface of the magnesium alloy has more excellent corrosion resistance and can effectively protect a magnesium matrix.
Example 3
A preparation method of a triple self-repairing SLIPS/LDHs composite film layer on the surface of a magnesium alloy comprises the following specific steps:
1. in-situ growth of MgAlLa-LDHs film
The magnesium alloy AZ31 after water grinding is soaked in the degreasing and degreasing aqueous solution (40 g/L of sodium hydroxide, 25g/L of sodium carbonate and 40g/L of sodium phosphate), the water bath is kept at 50 ℃ for 60 seconds, then is washed by 1M aqueous solution of sodium hydroxide 60 for 30 seconds, and then is polished for 1 to 2 minutes at room temperature and 25 ℃ by 400g/L of nitric acid. And then the mixture is washed once by deionized water and dried by cold air.
A hydrothermal reaction step: firstly, pouring electrolyte into a liner of a reaction kettle, and then placing a cleaned magnesium alloy sample into in-situ growth liquid, wherein the in-situ growth liquid is as follows: sodium nitrate 0.1M, aluminum nitrate 0.05M, lanthanum nitrate 0.001M, pH10.9; and (3) after the reaction kettle is closed, placing the reaction kettle into an electric oven for in-situ growth, wherein the reaction temperature is 125+/-5 ℃, and the constant-temperature reaction time is set to be 12 hours, so that the magnesium alloy with the ternary MgAlLa-LDHs film layer grown on the surface is obtained.
2. Supported corrosion inhibitor
Immersing the magnesium alloy sample in the step 1 into 0.3M sodium benzoate water solution, wherein the water bath temperature is 60+/-5 ℃, and the constant-temperature reaction time is set to be 2 hours.
3. Fluorinated layer
And (3) a fluorination treatment step: immersing the magnesium alloy sample in the step 2 into an absolute ethanol solution of 0.03M perfluorodecyl trimethoxysilane, wherein the water bath temperature is 60+/-5 ℃, and the constant-temperature reaction time is set to be 2 hours. After the reaction is completed, the mixture is washed with water and then dried.
4. Lubricating liquid layer
And (3) dropwise adding excessive perfluoropolyether to the surface of the magnesium alloy sample treated in the step (3), and inclining for 1 hour at an angle of 15+/-2 degrees to enable excessive lubricating liquid to flow out of the surface of the sample, so as to finally obtain the triple self-repairing SLIPS/LDHs composite film magnesium alloy. Further detecting the structure, the morphology and the like.
FIG. 7 is a scanning electron microscope photograph of the rear surface of a MgAlLa-LDHs film layer grown on a magnesium alloy. FIG. 8 is a scanning electron microscope photograph of the surface of SLIPS/LDHs composite film magnesium alloy. FIG. 9 is Tafil polarization curves of AZ31 magnesium alloy, mgAlLa-LDHs film magnesium alloy and SLIPS/LDHs composite film magnesium alloy at the same coordinates. Wherein the corrosion voltage of the pure AZ31 magnesium alloy is-1492+/-8 mV, the corrosion voltage of the MgAlLa-LDHs film magnesium alloy is-389+/-6 mV, the corrosion voltage of the triple self-repairing SLIPS/LDHs composite film prepared by the embodiment 3 is-917+/-3 mV, compared with the corrosion voltage of a magnesium alloy matrix, the corrosion inclination is reduced, and the corrosion speed and the corrosion resistance are directly related to the corrosion current density. The corrosion current density of the pure AZ31 magnesium alloy is 6.57×10 -5 Acm -2 The corrosion current density of the MgAlLa-LDHs film layer is 6.82 multiplied by 10 -7 Acm -2 The corrosion current density of SLIPS/LDHs composite film layer is 3.56×10 -9 Acm -2 The corrosion current density of the treated sample is respectively reduced by two and four orders of magnitude compared with that of a sample of the pure AZ31 magnesium alloy. The MgAlLa-LDHs film and SLIPS/LDHs composite film have effective corrosion inhibition effect on AZ31 magnesium alloy, and the SLIPS/LDHs composite film on the surface of the magnesium alloy has more excellent corrosion resistance and can effectively protect a magnesium matrix.
Example 4
A preparation method of a triple self-repairing SLIPS/LDHs composite film layer on the surface of a magnesium alloy comprises the following specific steps:
1. in-situ growth of MgAlLa-LDHs film
The magnesium alloy AZ31 after water milling is soaked in the degreasing and degreasing aqueous solution (40 g/L of sodium hydroxide, 25g/L of sodium carbonate and 40g/L of sodium phosphate), the water bath is kept at 50 ℃ for 60 seconds, then is washed with 1M aqueous solution of sodium hydroxide 60 for 30 seconds, and then is polished for 1-2 minutes at room temperature of 25 ℃ by 400g/L of nitric acid (rho=1.42 g/ml). And then the mixture is washed once by deionized water and dried by cold air.
A hydrothermal reaction step: firstly, pouring electrolyte into a liner of a reaction kettle, and then placing a cleaned magnesium alloy sample into in-situ growth liquid, wherein the in-situ growth liquid is as follows: sodium nitrate 0.1M, aluminum nitrate 0.05M, lanthanum nitrate 0.001M, pH10.9; and (3) after the reaction kettle is closed, placing the reaction kettle into an electric oven for in-situ growth, wherein the reaction temperature is 125+/-5 ℃, and the constant-temperature reaction time is set to be 12 hours, so that the magnesium alloy with the ternary MgAlLa-LDHs film layer grown on the surface is obtained.
2. Supported corrosion inhibitor
Immersing the magnesium alloy sample in the step 1 into 0.5M sodium benzoate water solution, wherein the water bath temperature is 60+/-5 ℃, and the constant-temperature reaction time is set to be 2 hours.
3. Fluorinated layer
And (3) a fluorination treatment step: immersing the magnesium alloy sample in the step 2 into an absolute ethanol solution of 0.05M perfluorodecyl trimethoxysilane, wherein the water bath temperature is 60+/-5 ℃, and the constant-temperature reaction time is set to be 2 hours. After the reaction is completed, the mixture is washed with water and then dried.
4. Lubricating liquid layer
And (3) dropwise adding excessive Krytox lubricating oil (DuPont) on the surface of the magnesium alloy sample treated in the step (3), and then tilting at an angle of 15+/-2 ℃ for 1 hour to enable the excessive lubricating liquid to flow out of the surface of the sample, so as to finally obtain the triple self-repairing SLIPS/LDHs composite film magnesium alloy. Further detecting the structure, the morphology and the like.
Fig. 10 is a scanning electron microscope photograph of the rear surface of the MgAlLa-LDHs film layer grown on the magnesium alloy. FIG. 11 is a scanning electron microscope photograph of the surface of SLIPS/LDHs composite film magnesium alloy. FIG. 12 is a Tafil polarization curve of AZ31 magnesium alloy, mgAlLa-LDHs film magnesium alloy and SLIPS/LDHs composite film magnesium alloy at the same coordinates. Wherein the corrosion voltage of the pure AZ31 magnesium alloy is-1479+/-7 mV, the corrosion voltage of the MgAlLa-LDHs film layer is-212+/-3 mV, the corrosion voltage of the triple self-repairing SLIPS/LDHs composite film layer prepared by the embodiment 4 is-715+/-5 mV, compared with the corrosion voltage of a magnesium alloy matrix, the corrosion inclination is reduced, and the corrosion speed and the corrosion resistance are directly related to the corrosion current density. Pure AZ3The corrosion current density of the 1 magnesium alloy is 6.52×10 -5 Acm -2 The corrosion current density of the MgAlLa-LDHs film layer is 8.15X10 -7 Acm -2 The corrosion current density of SLIPS/LDHs composite film layer is 1.45 multiplied by 10 -9 Acm -2 The corrosion current density of the treated sample is respectively reduced by two and four orders of magnitude compared with that of a sample of the pure AZ31 magnesium alloy. The MgAlLa-LDHs film and SLIPS/LDHs composite film have effective corrosion inhibition effect on AZ31 magnesium alloy, and the SLIPS/LDHs composite film on the surface of the magnesium alloy has more excellent corrosion resistance and can effectively protect a magnesium matrix.
Performance testing
The samples prepared in examples 1 to 4 were subjected to test tests such as water contact angle, corrosion resistance and the like, and the test methods were as follows:
water contact angle: 5 mu L of water drop is dripped on the surface of a magnesium alloy sample, a camera and a microscope lens are used for photographing the water drop, the Young-Laplace method is adopted for fitting the outline of the water drop, the calculation of the contact angle is carried out, and fig. 13 to 16 are water contact angle test diagrams of the embodiment 1 to the embodiment 4 respectively.
Corrosion resistance: the polarization curve of magnesium alloy samples in 3.5wt.% sodium chloride solution was tested by an electrochemical workstation (Princeton 4000A). The test results are shown in the following table:
TABLE 1 test results of SLIPS/LDHs composite film prepared in examples 1-4
Figure BDA0003175411020000081
Figure BDA0003175411020000091
The results show that the magnesium alloy surface SLIPS/LDHs composite film layer prepared by the method has good hydrophobicity and corrosion resistance, and has a large application prospect. The invention combines pouring liquid on the basis of the nano-layer lamellar structure of the layered double hydroxide (Layered Double Hydroxides, LDHs)Smooth porous surface (slip-infused porous surface). SLIPS is a novel surface of a super-hydrophobic membrane layer, and has good stability, hydrophobicity and self-repairing property. A layer of compact porous LDHs is grown on the surface of the magnesium alloy in situ and is used as a good nano container for containing lubricating liquid to construct SLIPS, so that the generated hydrophobicity can further effectively isolate the corrosion of the external corrosive environment to the magnesium alloy matrix and improve the corrosion resistance of the magnesium alloy. The invention constructs SLIPS by means of good nano-containers of ternary MgAlLa-LDHs to adsorb and store lubricating liquid; its unique ion exchange properties can also give active protection to the membrane layer (adsorption of Cl in corrosive solutions) - Ions) and smart repair (release of interlayer-loaded corrosion inhibitor anions). And the filling of SLIPS lubricating liquid is used for carrying out effective hole sealing on the LDHs film layer, so that the corrosion of external corrosive ions on the magnesium alloy is prevented. The two complement each other to finally prepare the SLIPS/LDHs composite film with excellent corrosion resistance.
Finally, it is noted that the above-mentioned preferred embodiments are only intended to illustrate rather than limit the invention, and that, although the invention has been described in detail by means of the above-mentioned preferred embodiments, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the invention as defined by the appended claims.

Claims (9)

1. The preparation method of the SLIPS/LDHs composite film on the surface of the magnesium alloy is characterized by comprising the following specific steps of:
a. firstly, growing a MgAlLa-LDHs film layer on the surface of the magnesium alloy in situ: immersing the cleaned magnesium alloy matrix into in-situ growth liquid, carrying out hydrothermal reaction for 12-16 hours at 110-130 ℃, taking out and washing with deionized water for multiple times to obtain magnesium alloy growing with MgAlLa-LDHs film layers; according to the mass concentration of the substances, the in-situ growth liquid is an aqueous solution of 0.02-0.1M of aluminum nitrate, 0.05-0.25M of sodium nitrate and 0.001M-0.025M of lanthanum nitrate, and the pH value is 9.5-12;
b. then immersing the magnesium alloy into 0.1M-0.5M sodium benzoate solution, reacting for 2-4 hours at 50-70 ℃;
c. fluorinated layer: immersing the magnesium alloy treated in the step b into anhydrous ethanol solution containing fluorine silane, carrying out fluorination treatment for 2-4 hours, cleaning and drying to obtain a fluorinated layer; the concentration of the fluorine-containing silane is 0.02M-0.05M;
d. lubricating liquid layer: and c, dripping the lubricating liquid on the surface of the magnesium alloy treated in the step c, and then obliquely placing the magnesium alloy at an angle of 10-20 degrees to enable the lubricating liquid to flow out of the surface of the magnesium alloy to form a lubricating liquid layer, so that the magnesium alloy with the SLIPS/LDHs composite film layer is finally obtained.
2. The method for preparing the magnesium alloy surface SLIPS/LDHs composite film layer according to claim 1, wherein the in-situ growth liquid is an aqueous solution of 0.05M of aluminum nitrate, 0.1M of sodium nitrate and 0.001M-0.025M of lanthanum nitrate, and the pH is 9.5-12.
3. The method for preparing the magnesium alloy surface SLIPS/LDHs composite film according to claim 1, wherein the pH of the in-situ growth liquid in the step a is 10.8-11.2.
4. The method for preparing a magnesium alloy surface SLIPS/LDHs composite film according to claim 1, wherein the loading of sodium benzoate in step b is performed in deionized water solution.
5. The method for preparing the magnesium alloy surface SLIPS/LDHs composite film according to claim 1, wherein the fluorine-containing silane is perfluorodecyl triethoxysilane or perfluorodecyl trimethoxysilane.
6. The method for preparing the magnesium alloy surface SLIPS/LDHs composite film according to claim 1, wherein the lubricating liquid is one or more selected from the group consisting of simethicone, krytox lubricating oil and perfluoropolyether.
7. The method for preparing a magnesium alloy surface SLIPS/LDHs composite film according to any one of claims 1-6, wherein the cleaning in step a is to clean the magnesium alloy surface with deionized water; or the surface of the magnesium alloy is firstly subjected to water grinding, degreasing and degreasing, and then is cleaned by deionized water.
8. The use of the method for preparing a magnesium alloy surface SLIPS/LDHs composite film according to any one of claims 1 to 7 in magnesium alloy surface treatment.
9. Use of the product obtained by the preparation method of the magnesium alloy surface SLIPS/LDHs composite film layer according to any one of claims 1-7 in the field of aerospace, automobiles or electronic products.
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