CN110093647B - Method for preparing layered double hydroxide corrosion-resistant coating on surface of magnesium and magnesium alloy in situ - Google Patents

Method for preparing layered double hydroxide corrosion-resistant coating on surface of magnesium and magnesium alloy in situ Download PDF

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CN110093647B
CN110093647B CN201910277494.0A CN201910277494A CN110093647B CN 110093647 B CN110093647 B CN 110093647B CN 201910277494 A CN201910277494 A CN 201910277494A CN 110093647 B CN110093647 B CN 110093647B
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magnesium
manganese
hydroxide
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CN110093647A (en
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刘宣勇
张冬冬
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Shanghai Institute of Ceramics of CAS
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    • 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
    • C25D5/48—After-treatment of electroplated surfaces
    • 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
    • C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
    • C25D9/12—Electrolytic coating other than with metals with inorganic materials by cathodic processes on light metals

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Abstract

The invention relates to a method for preparing a layered double hydroxide corrosion-resistant coating on the surface of magnesium and magnesium alloy in situ, which comprises the following steps: firstly, preparing a hydroxide coating of a metal A element on the surface of magnesium and magnesium alloy, and then converting the obtained hydroxide coating of the metal A element into a layered double hydroxide corrosion-resistant coating through chemical conversion; the A element in the hydroxide coating of the metal A element is one of Fe and Mn, and preferably the hydroxide coating of the metal A element is iron oxyhydroxide (FeO (OH) or manganese oxyhydroxide (MnO (OH)).

Description

Method for preparing layered double hydroxide corrosion-resistant coating on surface of magnesium and magnesium alloy in situ
Technical Field
The invention relates to a method for modifying the surface of magnesium and magnesium alloy materials, in particular to a surface modification mode which firstly constructs metal hydroxide (such as (FeO (OH)) or (MnO (OH))) on the surface of the materials through electrochemical deposition and further carries out hydrothermal treatment on samples after the electrochemical deposition in water to form a layered double hydroxide corrosion-resistant coating, belonging to the technical field of surface modification of metal materials.
Background
The density of magnesium is 1.738g/cm3Belongs to a light metal material and has better noise absorption, shock absorption and radiation protection performance. Therefore, magnesium and its alloy materialPlays an important role in the aerospace industry, the military industry field, the traffic field and the like. In addition, in the field of medical metal materials, magnesium and magnesium alloy are expected to become the next-generation medical metal materials due to complete degradability. However, magnesium has a too low electrochemical potential and is highly susceptible to corrosion in humid air or in aqueous solutions. For the fields of aerospace, war industry and traffic, too fast corrosion causes great potential safety hazard in magnesium alloy construction. For medical magnesium alloy metal materials, too fast corrosion causes the implant to lose mechanical properties prematurely, and hydrogen gas cavities and alkaline microenvironment are generated around the implant, eventually leading to implant failure.
Surface modification of magnesium and its alloys is a common method to improve its corrosion resistance. In recent years, the use of layered double hydroxide coatings in the field of corrosion protection of metals has attracted the attention of many researchers. Furthermore, it has been shown that magnesium-aluminum layered double hydroxide (Mg-Al LDH) coating prepared by hydrothermal treatment can improve the corrosion resistance of magnesium alloy by using its unique ion exchange performance (see document 1: ACS appl. Mater. interfaces,2016,8(51), 35033-.
The prior art for preparing the layered double hydroxide coating by in-situ growth on the surface of the magnesium alloy mainly comprises direct hydrothermal treatment and a vapor coating method. The direct hydrothermal treatment refers to adding the magnesium substrate into an alkaline solution containing trivalent ions, then placing the magnesium substrate into a high-temperature reaction kettle, and reacting at high temperature and high pressure to obtain the magnesium substrate. In contrast to the direct hydrothermal method, the vapor coating method is to place the magnesium alloy on top of the reaction solution and then corrode the surface of the magnesium alloy with the water vapor generated at high temperature and high pressure in a high temperature reaction kettle to generate layered double hydroxide. However, both of the above methods are only suitable for preparing Mg-Al layered double hydroxide, and the prepared coating often contains magnesium hydroxide phase which is not good for improving corrosion resistance (see document 2: J Mater. Sci. Technol.,2018,34,1455-1466), and the corrosion resistance is poor.
Disclosure of Invention
Because the layered double hydroxide coating has great application prospect in the field of metal material corrosion resistance, in order to solve the problem of poor corrosion resistance of the existing magnesium and alloy materials thereof, the invention aims to provide a method for constructing the layered double hydroxide corrosion resistance coating on the surface of magnesium and alloy thereof in situ, which comprises the following steps: firstly, preparing a hydroxide coating of a metal A element on the surface of magnesium and magnesium alloy, and then converting the obtained hydroxide coating of the metal A element into a layered double hydroxide corrosion-resistant coating (Mg/A layered double hydroxide) through chemical conversion; the A element in the hydroxide coating of the metal A element is one of Fe and Mn, and preferably the hydroxide coating of the metal A element is iron oxyhydroxide (FeO (OH)) or manganese oxyhydroxide (MnO (OH)).
In the present disclosure, the process of preparing the layered double hydroxide corrosion resistant coating on the surface of magnesium and its alloy in situ comprises: the synthesis of metal hydroxide coatings, and chemical conversion processes.
Preferably, magnesium and its alloy are used as cathode, at least one of graphite, stainless steel and platinum is used as anode, and the hydroxide coating of metal A element is prepared on the surface of magnesium and its alloy by electrodeposition technology. For example, in the present invention, metal hydroxide (FeO (OH) or MnO (OH)) is prepared on the surface of magnesium and its alloy by using electrochemical deposition technology. The synthesis process of the metal hydroxide coating is completed through electrochemical deposition, the obtained metal hydroxide coating is in an amorphous state, and metal ions are in a trivalent state.
Preferably, when the hydroxide coating of the metal a element is iron oxyhydroxide (feo (oh)), the parameters of the electrodeposition technique include: the electrolyte is 0.50-1.00 g/L ferric nitrate and/or ferric chloride solution (containing at least one of ferric nitrate and ferric chloride), the solvent is absolute ethyl alcohol, the voltage is 100-120V, and the time is 1-3 minutes.
Also, preferably, the parameters of the electrodeposition technique include: the electrolyte is 0.75-1.00 g/L ferric nitrate and/or ferric chloride solution, absolute ethyl alcohol is used as a solvent, the voltage is 110-120V, and the time is 1-2 minutes; preferably: the electrolyte is 0.80-1.00 g/L ferric nitrate solution, the solvent is absolute ethyl alcohol, the voltage is 110-120V, and the time is 1-2 minutes.
Preferably, when the hydroxide coating of the metal a element is manganese oxyhydroxide (mno (oh)), the parameters of the electrodeposition technique include: the electrolyte is 1.00-5.00 g/L manganese chloride and/or manganese nitrate solution (containing at least one of manganese chloride and manganese nitrate), the solvent is absolute ethyl alcohol, the voltage is 25-120V, and the time is 10-60 seconds.
Also, preferably, the parameters of the electrodeposition technique include: 1.00-3.00 g/L of manganese chloride and/or manganese nitrate solution of electrolyte, absolute ethyl alcohol as solvent, 25-80V of voltage and 10-60 seconds of time; preferably: the electrolyte is a manganese chloride solution with the concentration of 1.00-2.00 g/L, the voltage is 1.00-2.00 g/L, and the time is 10-60 seconds.
Preferably, the chemical transformation comprises: placing magnesium and magnesium alloy with the surface prepared with the hydroxide coating of the metal A element into water for hydrothermal treatment. In the subsequent hydrothermal process, magnesium ions generated by magnesium and magnesium alloy react with the metal hydroxide coating prepared by electrodeposition to form a layered double hydroxide coating on the surface of the magnesium base in situ. For example, prepared samples (magnesium and its alloys having a coating of metal hydroxide (FeO (OH) or MnO (OH)) on the surface) are subjected to a hydrothermal treatment in water (pure or deionized water) in which magnesium ions generated from the magnesium substrate react with the electrodeposited metal hydroxide coating, during which reaction magnesium ions diffuse into the metal hydroxide coating and displace trivalent metal cations of the metal hydroxide, thereby causing the metal hydroxide to have a positive charge, and to balance these positive charges, some anions (e.g., OH) in the hydrothermal medium-) It is attracted into the metal hydroxide coating layers replaced by magnesium ions to form a layered structure, which forms a layered double hydroxide (Mg-Fe LDH or Mg-Mn LDH) coating layer in situ on the surface of the magnesium base.
Preferably, when the hydroxide coating of the metal A element is ferric oxyhydroxide (FeO (OH)), the temperature of the hydrothermal treatment is 90-120 ℃ and the time is 4-6 hours; preferably, the temperature of the hydrothermal treatment is 100-120 ℃, and the time is 4-5 hours; more preferably, the temperature of the hydrothermal treatment is 110-120 ℃ and the time is 4-5 hours.
Preferably, when the hydroxide coating of the metal A element is manganese oxyhydroxide (MnO (OH)), the temperature of the hydrothermal treatment is 50-80 ℃ and the time is 3-5 hours; preferably, the temperature of the hydrothermal treatment is 50-60 ℃ and the time is 4-5 hours; more preferably, the temperature of the hydrothermal treatment is 50-55 ℃ and the time is 4-5 hours.
In another aspect, the present invention also provides a layered double hydroxide corrosion resistant coating prepared in situ on the surface of magnesium and its alloys according to the above method. Wherein, the layered double hydroxide corrosion resistant coating can be a magnesium-iron layered double hydroxide coating and a magnesium-manganese layered double hydroxide coating. The thickness of the obtained layered double hydroxide corrosion-resistant coating can be 0.8-3.7 μm.
The method provided by the invention has the following advantages:
(1) the experiment does not need complex equipment, the experimental process is relatively safe, and the large-scale industrialization is facilitated;
(2) compared with the surface coating of magnesium and magnesium alloy prepared by other methods, the coating provided by the invention has the following advantages: the coating and the substrate are bonded in situ, and the bonding force is strong. The magnesium-iron layered double hydroxide has excellent properties (such as degradability, drug-loading capacity, good biocompatibility, rich functional groups and the like) so that the coating can be applied in various aspects;
(3) the prepared layered double hydroxide coating with strong binding force can be directly used as an anti-corrosion coating on the surface of magnesium and magnesium alloy or used as a pretreatment layer, and is expected to be applied to the fields of aerospace, traffic, medical metal materials and the like.
Drawings
FIG. 1 is a scanning electron microscope image provided by the present invention: untreated magnesium substrate (a), electrochemically deposited iron oxyhydroxide (feo (oh)) (b) in example 1, electrochemically deposited manganese oxyhydroxide (mno (oh)) (c) in example 9, hydrothermally formed magnesium iron layered double hydroxide (d) in example 1, and hydrothermally formed magnesium manganese layered double hydroxide (e) in example 9; it can be seen from fig. 1 that the layered double hydroxide formed is in a sheet-like nanostructure;
FIG. 2 is an infrared spectrum (a) of a powder test conducted by scraping off the surface of a sample of iron oxyhydroxide (FeO (OH)) after electrochemical deposition in example 1 provided by the present invention; x-ray photoelectron spectra (b, c and d) of the sample; thermal analysis (test conditions: temperature increase rate of 10 ℃/min, measurement range of room temperature to 600 ℃) diagram (e) and X-ray diffraction diagram (f) of the powder; as can be seen from fig. 2: the infrared spectrogram shows that Fe-OH-Fe and Fe-O bonds exist in the test sample; the X-ray photoelectron spectrum indicates that Fe-O-H and Fe-O-Fe exist in the test sample; the thermal analysis and X-ray diffraction pattern show that the oxygen is amorphous FeO (OH) before the test, and the product is alpha-Fe after the test2O3_) And the weight loss rate of the test sample is close to the theoretical weight loss rate of FeO (OH) of the iron oxyhydroxide, so that the iron oxyhydroxide (FeO (OH)) is generated on the surface of the sample after electrochemical deposition;
FIG. 3 is an infrared spectrum (a) of a powder test conducted after electrochemically depositing manganese (MnO) (OH) hydroxide in example 9 and scraping off the surface of a sample thereof; x-ray photoelectron spectra (b, c and d) of the sample; thermal analysis (test conditions: temperature increase rate of 10 ℃/min, measurement range of room temperature to 600 ℃) diagram (e) and X-ray diffraction diagram (f) of the powder; as can be seen from fig. 3: the infrared spectrogram shows that Mn-OH and Mn-O bonds exist in the test sample; the X-ray photoelectron spectroscopy indicates the presence of trivalent manganese in the test sample; the thermal analysis and X-ray diffraction pattern show that the sample is amorphous MnO (OH) before test, and the product is alpha-Mn after test2O3) And the weight loss rate of the test sample is close to the theoretical weight loss rate of the manganese oxyhydroxide (MnO) (OH), so that the manganese oxyhydroxide (MnO) (OH) is generated on the surface of the sample after electrochemical deposition;
FIG. 4 is an X-ray diffraction pattern of an untreated magnesium substrate, the magnesium iron layered double hydroxide prepared in example 1, and the magnesium manganese layered double hydroxide prepared in example 9 provided by the present invention, showing formation of LDH phases on the surface of the coating;
FIG. 5 shows the profile of the magnesium-manganese layered double hydroxide prepared in examples 9-10 (left), the energy spectrum of the surface distribution of Mg (middle), and the energy spectrum of the surface distribution of Mn (right), wherein (d) shows example 9, and (e) shows example 10, which shows that the coating has no distinct interface with the substrate and is well bonded, and the thickness of the coating is 0.8-2.5 μm;
fig. 6 is a polarization curve diagram (measured in 80mL PBS solution, using CH1760C three-electrode electrochemical workstation) of an untreated magnesium alloy sample according to the present invention and a magnesium-iron layered double hydroxide (a) prepared in example 1 and a magnesium-manganese layered double hydroxide (b) prepared in example 9, respectively, and it can be seen that the corrosion resistance of the magnesium alloy surface-modified by the layered double hydroxide can be significantly improved;
fig. 7 is a sectional view (left diagram) of the magnesium-iron layered double hydroxide prepared in examples 1 to 3, an energy spectrum (middle diagram) of the surface distribution of Mg element, and an energy spectrum (right diagram) of the surface distribution of Fe element provided in the present invention, where (a) is example 1, (b) is example 2, and (c) is example 3, it can be seen that the coating has no distinct interface with the substrate, the bonding is good, and the thickness of the magnesium-iron layered double hydroxide coating is 1.8 to 3.7 μm.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative and not restrictive.
In the disclosure, a Layer of metal hydroxide coating (hydroxide coating of metal element a) is prepared on the surface of pure magnesium or its alloy for the first time, and the prepared metal hydroxide is further converted (reacted) by chemical conversion, so as to obtain a Mg/a Layered Double Hydroxide (LDH) corrosion-resistant coating. Wherein, the A element can be one of Fe and Mn. For example, the metal hydroxide produced may be iron oxyhydroxide (FeO (OH)), or manganese oxyhydroxide (MnO (OH)). For example, the resulting Mg/A layered double hydroxide may be a magnesium/iron layered double hydroxide Mg-Fe LDH, or a magnesium/manganese layered double hydroxide Mg-Mn LDH. The layered double hydroxide coating prepared by the method can obviously improve the corrosion resistance of magnesium and magnesium alloy, and is expected to be applied to the field of magnesium alloy surface modification.
In an alternative embodiment, the metal hydroxide coating preparation process may be accomplished by electrochemical deposition. Specifically, magnesium and magnesium alloy are used as a cathode, at least one of graphite, stainless steel and metal platinum is used as an anode, and a metal hydroxide coating is prepared on the surface of the magnesium and magnesium alloy by using an electrodeposition technology.
In an alternative embodiment, the metal hydroxide chemical conversion process may be accomplished by hydrothermal treatment. Wherein, the solvent of the hydrothermal treatment can be pure water or deionized water.
When the metal hydroxide is iron oxyhydroxide (feo (oh)), the experimental conditions for electrochemical deposition during the preparation of iron oxyhydroxide (feo (oh)) may be: the electrolyte is 0.50-1.00 g/L ferric nitrate and/or ferric chloride solution, the solvent is absolute ethyl alcohol, the voltage is 100-120V, and the time is 1-3 min. Preferred experimental conditions may be: the electrolyte is 0.75-1.00 g/L ferric nitrate and/or ferric chloride solution, and the solvent is absolute ethyl alcohol, the voltage is 110-120V, and the time is 1-2 min. More preferred experimental conditions may be: the electrolyte is 0.80-1.00 g/L ferric nitrate solution, the solvent is absolute ethyl alcohol, the voltage is 110-120V, and the time is 1-2 min.
When the metal hydroxide is manganese oxyhydroxide (mno (oh)), experimental conditions for electrochemical deposition during the preparation of iron oxyhydroxide (feo (oh)) may be: the electrolyte is a manganese chloride and/or manganese nitrate solution with the concentration of 1.00-5.00 g/L, the solvent is absolute ethyl alcohol, the voltage is 25-120V, and the time is 10-60 s. Preferred experimental conditions may be: 1.00-3.00 g/L of manganese chloride and/or manganese nitrate solution of electrolyte, absolute ethyl alcohol as solvent, 25-80V of voltage and 10-60 s of time. More preferred experimental conditions may be: the electrolyte is a manganese chloride solution with the concentration of 1.00-2.00 g/L, the voltage is 1.00-2.00 g/L, and the time is 10-60 s.
When the layered double hydroxide is magnesium/iron layered double hydroxide, in the preparation process of the magnesium-iron layered double hydroxide, the metal hydroxide is ferric oxyhydroxide (feo (oh)), and the experimental conditions of the hydrothermal treatment can be as follows: the hydrothermal medium is pure water and/or deionized water, the temperature is 90-120 ℃, and the time is 4-6 h. The higher the hydrothermal temperature, the shorter the time to form the coating. Preferred experimental conditions may be: the hydrothermal medium is pure water and/or deionized water, the temperature is 100-120 ℃, and the time is 4-5 hours. More preferred experimental conditions may be: the hydrothermal medium is pure water and/or deionized water, the temperature is 110-120 ℃, and the time is 4-5 hours.
When the layered double hydroxide is magnesium/manganese layered double hydroxide, in the preparation process of the magnesium-manganese layered double hydroxide, the metal hydroxide is manganese oxyhydroxide (MnO (OH)), and the experimental conditions of the hydrothermal treatment can be as follows: the hydrothermal medium is pure water and/or deionized water, the temperature is 50-80 ℃, and the time is 3-5 hours. The longer the hydrothermal time, the better the crystallinity of the resulting coating. Preferred experimental conditions may be: the hydrothermal medium is pure water and/or deionized water, the temperature is 50-60 ℃, and the more preferable experimental conditions for 4-5 hours can be as follows: the hydrothermal medium is pure water and/or deionized water, the temperature is 50-55 ℃, and the time is 4-5 hours.
In one embodiment of the present invention, a metal hydroxide coating is first prepared on the surface of pure magnesium or its alloy by electrodeposition, and then the electrodeposited sample is hydrothermally treated in pure water, during which magnesium ions generated from the magnesium substrate react with the electrodeposited metal hydroxide coating to form a layered double hydroxide in situ on the surface of the magnesium substrate.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
(a) Preparing 1.00g/L ferric nitrate solution by using absolute ethyl alcohol as electrolyte;
(b) taking magnesium alloy as a cathode and graphite as an anode, and keeping the voltage at 120V for 1 min;
(c) and carrying out hydrothermal treatment on the electrodeposited sample in pure water, wherein the temperature of the hydrothermal treatment is 90 ℃ and the time is 6 hours. X-ray diffraction analysis indicated that LDH phase was formed on the surface of the coating. Comparison of the polarization curves shows that the LDH coating significantly improves the corrosion resistance of the sample.
Example 2
(a) Preparing 1.00g/L ferric nitrate solution by using absolute ethyl alcohol as electrolyte;
(b) taking magnesium alloy as a cathode and graphite as an anode, and keeping the voltage at 120V for 2 min;
(c) and carrying out hydrothermal treatment on the electrodeposited sample in pure water, wherein the temperature of the hydrothermal treatment is 105 ℃, and the time is 5 hours. X-ray diffraction analysis indicated that LDH phase was formed on the surface of the coating. Comparison of the polarization curves shows that the LDH coating significantly improves the corrosion resistance of the sample.
Example 3
(a) Preparing 1.00g/L ferric nitrate solution by using absolute ethyl alcohol as electrolyte;
(b) taking magnesium alloy as a cathode and graphite as an anode, and keeping the voltage at 120V for 3 min;
(c) and carrying out hydrothermal treatment on the electrodeposited sample in pure water, wherein the temperature of the hydrothermal treatment is 105 ℃, and the time is 5 hours. X-ray diffraction analysis indicated that LDH phase was formed on the surface of the coating. Comparison of the polarization curves shows that the LDH coating significantly improves the corrosion resistance of the sample.
Example 4
(a) Preparing 1.00g/L ferric nitrate solution by using absolute ethyl alcohol as electrolyte;
(b) taking magnesium alloy as a cathode and graphite as an anode, and keeping the voltage at 120V for 1 min;
(c) and carrying out hydrothermal treatment on the electrodeposited sample in pure water, wherein the temperature of the hydrothermal treatment is 105 ℃, and the time is 4 hours. X-ray diffraction analysis indicated that LDH phase was formed on the surface of the coating. Comparison of the polarization curves shows that the LDH coating significantly improves the corrosion resistance of the sample.
Example 5
(a) Preparing 1.00g/L ferric nitrate solution by using absolute ethyl alcohol as electrolyte;
(b) taking magnesium alloy as a cathode and graphite as an anode, and keeping the voltage at 100V for 1 min;
(c) and carrying out hydrothermal treatment on the electrodeposited sample in pure water, wherein the temperature of the hydrothermal treatment is 105 ℃, and the time is 5 hours. X-ray diffraction analysis indicated that LDH phase was formed on the surface of the coating. Comparison of the polarization curves shows that the LDH coating significantly improves the corrosion resistance of the sample.
Example 6
(a) Preparing 1.00g/L ferric nitrate solution by using absolute ethyl alcohol as electrolyte;
(b) taking magnesium alloy as a cathode and graphite as an anode, and keeping the voltage at 110V for 1 min;
(c) and carrying out hydrothermal treatment on the electrodeposited sample in pure water, wherein the temperature of the hydrothermal treatment is 105 ℃, and the time is 5 hours. X-ray diffraction analysis indicated that LDH phase was formed on the surface of the coating. Comparison of the polarization curves shows that the LDH coating significantly improves the corrosion resistance of the sample.
Example 7
(a) Preparing 0.75g/L ferric nitrate solution by using absolute ethyl alcohol to serve as electrolyte;
(b) taking magnesium alloy as a cathode and graphite as an anode, and keeping the voltage at 120V for 1 min;
(c) and carrying out hydrothermal treatment on the electrodeposited sample in pure water, wherein the temperature of the hydrothermal treatment is 105 ℃, and the time is 5 hours. X-ray diffraction analysis indicated that LDH phase was formed on the surface of the coating. Comparison of the polarization curves shows that the LDH coating significantly improves the corrosion resistance of the sample.
Example 8
(a) Preparing 0.50g/L ferric nitrate solution by using absolute ethyl alcohol to serve as electrolyte;
(b) taking magnesium alloy as a cathode and graphite as an anode, and keeping the voltage at 120V for 1 min;
(c) and carrying out hydrothermal treatment on the electrodeposited sample in pure water, wherein the temperature of the hydrothermal treatment is 105 ℃, and the time is 5 hours. X-ray diffraction analysis indicated that LDH phase was formed on the surface of the coating. Comparison of the polarization curves shows that the LDH coating significantly improves the corrosion resistance of the sample.
Example 9
(a) Preparing 5.00g/L manganese chloride solution by using absolute ethyl alcohol as electrolyte;
(b) taking magnesium alloy as a cathode and graphite as an anode, and keeping the voltage at 25V for 20 s;
(c) and carrying out hydrothermal treatment on the electrodeposited sample in pure water, wherein the temperature of the hydrothermal treatment is 50 ℃ and the time is 5 hours. X-ray diffraction analysis indicated that LDH phase was formed on the surface of the coating. Comparison of the polarization curves shows that the LDH coating significantly improves the corrosion resistance of the sample.
Example 10
(a) Preparing 5.00g/L manganese chloride solution by using absolute ethyl alcohol as electrolyte;
(b) taking magnesium alloy as a cathode and graphite as an anode, and keeping the voltage at 25V for 60 s;
(c) and carrying out hydrothermal treatment on the electrodeposited sample in pure water, wherein the temperature of the hydrothermal treatment is 50 ℃ and the time is 5 hours. X-ray diffraction analysis indicated that LDH phase was formed on the surface of the coating. Comparison of the polarization curves shows that the LDH coating significantly improves the corrosion resistance of the sample.
Example 11
(a) Preparing 5.00g/L manganese chloride solution by using absolute ethyl alcohol as electrolyte;
(b) taking magnesium alloy as a cathode and graphite as an anode, and keeping the voltage at 25V for 20 s;
(c) and carrying out hydrothermal treatment on the electrodeposited sample in pure water, wherein the temperature of the hydrothermal treatment is 65 ℃ and the time is 4 hours. X-ray diffraction analysis indicated that LDH phase was formed on the surface of the coating. Comparison of the polarization curves shows that the LDH coating significantly improves the corrosion resistance of the sample.
Example 12
(a) Preparing 5.00g/L manganese chloride solution by using absolute ethyl alcohol as electrolyte;
(b) taking magnesium alloy as a cathode and graphite as an anode, and keeping the voltage at 25V for 20 s;
(c) and carrying out hydrothermal treatment on the electrodeposited sample in pure water, wherein the temperature of the hydrothermal treatment is 80 ℃, and the time is 4 hours. X-ray diffraction analysis indicated that LDH phase was formed on the surface of the coating. Comparison of the polarization curves shows that the LDH coating significantly improves the corrosion resistance of the sample.
Example 13
(a) Preparing 1.00g/L manganese chloride solution as electrolyte by using absolute ethyl alcohol;
(b) taking magnesium alloy as a cathode and graphite as an anode, and keeping the voltage at 120V for 10 s;
(c) and carrying out hydrothermal treatment on the electrodeposited sample in pure water, wherein the temperature of the hydrothermal treatment is 50 ℃ and the time is 5 hours. X-ray diffraction analysis indicated that LDH phase was formed on the surface of the coating. Comparison of the polarization curves shows that the LDH coating significantly improves the corrosion resistance of the sample.
Example 14
(a) Preparing 2.00g/L manganese chloride solution by using absolute ethyl alcohol as electrolyte;
(b) taking magnesium alloy as a cathode and graphite as an anode, and keeping the voltage at 100V for 10 s;
(c) and carrying out hydrothermal treatment on the electrodeposited sample in pure water, wherein the temperature of the hydrothermal treatment is 50 ℃ and the time is 5 hours. X-ray diffraction analysis indicated that LDH phase was formed on the surface of the coating. Comparison of the polarization curves shows that the LDH coating significantly improves the corrosion resistance of the sample.

Claims (10)

1. A method for preparing a layered double hydroxide corrosion-resistant coating on the surface of magnesium and magnesium alloy in situ is characterized in that firstly, magnesium and magnesium alloy are used as a cathode, at least one of graphite, stainless steel and metal platinum is used as an anode, a hydroxide coating of a metal A element is prepared on the surface of magnesium and magnesium alloy by utilizing an electrodeposition technology, and then the obtained hydroxide coating of the metal A element is converted into the layered double hydroxide corrosion-resistant coating by hydrothermal treatment in pure water or deionized water; the A element in the hydroxide coating of the metal A element is one of Fe and Mn, and the hydroxide coating of the metal A element is iron oxyhydroxide (FeO (OH)) or manganese oxyhydroxide (MnO (OH));
when the hydroxide coating of the metal A element is ferric oxyhydroxide (FeO (OH)), the parameters of the electrodeposition technology are as follows: the electrolyte is 0.50-1.00 g/L ferric nitrate solution, 0.50-1.00 g/L ferric chloride solution or 0.50-1.00 g/L ferric nitrate and ferric chloride solution, the solvent is absolute ethyl alcohol, the voltage is 100-120V, and the time is 1-3 minutes;
when the hydroxide coating of the metal A element is manganese oxyhydroxide (MnO (OH)), the parameters of the electrodeposition technology are as follows: the electrolyte is a manganese chloride solution of 1.00-5.00 g/L, a manganese nitrate solution of 1.00-5.00 g/L or a manganese chloride and manganese nitrate solution of 1.00-5.00 g/L, the solvent is absolute ethyl alcohol, the voltage is 25-120V, and the time is 10-60 seconds;
when the hydroxide coating of the metal A element is FeO (OH), the hydrothermal treatment temperature is 90-120 ℃, and the time is 4-6 hours;
when the hydroxide coating of the metal A element is manganese oxyhydroxide (MnO (OH)), the temperature of the hydrothermal treatment is 50-80 ℃ and the time is 3-5 hours.
2. The method according to claim 1, characterized in that, when the hydroxide coating of the metal a element is iron oxyhydroxide (feo (oh)), the parameters of the electrodeposition technique are: the electrolyte is 0.75-1.00 g/L ferric nitrate solution, 0.75-1.00 g/L ferric chloride solution or 0.75-1.00 g/L ferric nitrate and ferric chloride solution, the solvent is absolute ethyl alcohol, the voltage is 110-120V, and the time is 1-2 minutes.
3. The method according to claim 2, characterized in that, when the hydroxide coating of the metal a element is iron oxyhydroxide (feo (oh)), the parameters of the electrodeposition technique are: the electrolyte is 0.80-1.00 g/L ferric nitrate solution, the solvent is absolute ethyl alcohol, the voltage is 110-120V, and the time is 1-2 minutes.
4. The method of claim 1, wherein when the hydroxide coating of metal a is manganese oxyhydroxide (mno (oh)), the electrodeposition technique parameters are: 1.00-3.00 g/L of manganese chloride solution, 1.00-3.00 g/L of manganese nitrate solution or 1.00-3.00 g/L of manganese chloride and manganese nitrate solution, wherein the solvent is absolute ethyl alcohol, the voltage is 25-80V, and the time is 10-60 seconds.
5. The method of claim 4, wherein when the hydroxide coating of metal A is manganese oxyhydroxide (MnO (OH)), the electrodeposition technique parameters are: the electrolyte is 1.00-2.00 g/L manganese chloride solution, the voltage is 25-80V, and the time is 10-60 seconds.
6. The method according to claim 1, wherein when the hydroxide coating of the metal A element is iron oxyhydroxide (FeO (OH)), the hydrothermal treatment is performed at a temperature of 100 to 120 ℃ for 4 to 5 hours.
7. The method according to claim 6, wherein when the hydroxide coating of the metal A element is iron oxyhydroxide (FeO (OH)), the hydrothermal treatment is performed at a temperature of 110 to 120 ℃ for 4 to 5 hours.
8. The method of claim 1, wherein when the hydroxide coating of metal A is manganese oxyhydroxide (MnO (OH)), the hydrothermal treatment is performed at a temperature of 50 to 60 ℃ for 4 to 5 hours.
9. The method of claim 8, wherein when the hydroxide coating of metal A is manganese oxyhydroxide (MnO (OH)), the hydrothermal treatment is performed at a temperature of 50 to 55 ℃ for 4 to 5 hours.
10. A layered double hydroxide corrosion resistant coating prepared in situ on the surface of magnesium and its alloys according to the method of any one of claims 1-9.
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