MXene-Ni-C-ODD, corrosion-resistant modified waterborne epoxy resin coating prepared from MXene-Ni-C-ODD and application

Abstract

The invention belongs to the technical field of metal matrix surface coating protection, and discloses MXene-Ni-C-ODD, a corrosion-resistant modified waterborne epoxy resin coating prepared from the MXene-Ni-C-ODD and application of the MXene-Ni-C-ODD, the MXene-Ni-C-ODD is abbreviated as mMO, a nickel source and an organic ligand are mixed and then added into a solvent to be dissolved, then MXene suspension liquid is added, hydrothermal treatment is carried out at the temperature of 80-180 DEG C, MOFs-MXene is prepared, MXene-Ni-C is obtained through annealing at the temperature of 200-800 DEG C, and the MXene-Ni-C-ODD is prepared. And then adding into a heptadecenylaminoethyl imidazoline quaternary ammonium salt (ODD) solution, and precipitating and drying to obtain the product. MXene-Ni-C-ODD with magnetism is added into waterborne epoxy resin, curing is carried out after magnetic regulation and control, the modified waterborne epoxy resin coating is prepared on the surface of a metal matrix, and the modified waterborne epoxy resin coating has physical shielding, self-healing performance and corrosion resistance and can be widely applied to the field of metal surface protection.

Description

Technical Field

[0001] The present invention belongs to the technical field of surface coating protection of metal matrixes, and specifically relates to MXene-Ni@C-ODD, a corrosion-resistant modified waterborne epoxy resin coating prepared therefrom, and applications thereof. Background Art

[0002] Due to excellent mechanical properties, good plasticity and other excellent properties, steel materials are widely used in fields such as construction and mechanical manufacturing. However, due to the presence of corrosive media in the environment, steel materials are extremely vulnerable to corrosion, resulting in the failure of the functions of steel materials, shortened service life, serious economic losses, and great safety problems. Therefore, research shows that coating an organic coating on the material surface is a good anti-corrosion strategy. An organic coating refers to a protective coating with specific functions covered on the surface of a matrix material, and has various advantages such as corrosion resistance, wear resistance, friction reduction, and heat resistance.

[0003] The organic coating can isolate the material from the corrosive media in the environment and prevent the electrochemical corrosion of the material. Among them, the waterborne epoxy resin coating is widely used in fields such as construction, food processing equipment, electronic and electrical equipment, and medical devices due to its environmental friendliness, non-toxicity, convenient construction, strong adhesion and other advantages. However, compared with the oil-based waterborne epoxy resin coating, the waterborne epoxy resin coating has problems such as low durability, poor mechanical properties, and easy cracking during the curing process, greatly shortening the service life of the material in a corrosive environment. In past improvement strategies, for example, sacrificial anode materials, corrosion inhibitors, shape memory polymers, or two-dimensional materials are added to protect the matrix. These two-dimensional materials play a powerful physical shielding role during the corrosion process, but the usually filled two-dimensional materials are prone to agglomeration in the coating, or the orientation distribution is difficult to be all parallel to the substrate, making it difficult to fully exert their physical shielding role. In addition, there is also the problem of weak self-healing ability after cracking. The existence of the above problems makes it unable to effectively protect the matrix. Summary of the Invention

[0004] In order to solve the deficiencies of the above-mentioned prior art, the purpose of the present invention is to provide MXene-Ni@C-ODD; the MXene-Ni@C-ODD has paramagnetism.

[0005] Another purpose of the present invention is to provide a corrosion-resistant modified waterborne epoxy resin coating prepared from the above-mentioned MXene-Ni@C-ODD and a preparation method thereof. The modified waterborne epoxy resin coating is prepared by combining magnetically treated MXene-Ni@C-ODD with waterborne epoxy resin on the surface of a matrix. It is not easy to crack, has a good physical shielding effect in a corrosive environment, releases a corrosion inhibitor when the waterborne epoxy resin coating is ruptured, and enables the waterborne epoxy resin coating to have strong self-healing ability and corrosion resistance.

[0006] Another object of the present invention is to provide the application of the above-mentioned MXene-Ni@C-ODD.

[0007] The object of the present invention is achieved by the following technical solutions:

[0008] A kind of MXene-Ni@C-ODD is abbreviated as mMO. The MXene-Ni@C-ODD is prepared by dissolving a nickel source and an organic ligand in a solvent, then adding an MXene suspension, performing hydrothermal treatment at 80-180 °C, collecting the precipitate and drying to obtain MOFs-MXene, annealing at 200-800 °C to obtain MXene-Ni@C, and then adding MXene-Ni@C into a corrosion inhibitor solution of heptadecenylamine ethyl imidazoline quaternary ammonium salt to load the corrosion inhibitor on MXene-Ni@C, collecting the precipitate and drying.

[0009] Preferably, the nickel source is NiCl2·6H2O, Ni(NO3)2·6H2O, NiSO4·6H2O or Ni(OAc)2·4H2O, and the organic ligand is 2,3,6,7,10,11-hexahydroxy triphenylene hydrate, phthalic acid, terephthalic acid, 1,3,5-benzenetricarboxylic acid or TDC (thiophene-2,5-dicarboxylic acid) benzenetricarboxylic acid; the solvent is DMF, water or ethanol.

[0010] Preferably, the mass ratio of the nickel source, the organic ligand and the solvent is (1-10):(1-10):(1-10); the mass ratio of MXene and MOFs in the MOFs-MXene is (1-10):(1-10); the mass ratio of MXene-Ni@C to heptadecenylamine ethyl imidazoline quaternary ammonium salt in the heptadecenylamine ethyl imidazoline quaternary ammonium salt solution is (1-10):1.

[0011] Preferably, the MXene is Ti3C2T x , Ta4C3T x , TiN3T x , V2CT x , Nb2CT x , Ti3CNT x , where x represents the total number of surface functional groups of the material, x = 1-3; the concentration of the MXene suspension is 0.1-10 mg / mL; the concentration of the heptadecenylamine ethyl imidazoline quaternary ammonium salt corrosion inhibitor solution is 1-100 wt.%.

[0012] A corrosion-resistant modified waterborne epoxy resin coating is prepared with the above-mentioned MXene-Ni@C-ODD.

[0013] The preparation method of the corrosion-resistant modified waterborne epoxy resin coating includes the following steps;

[0014] S1. Degrease the metal substrate with acetone or absolute ethanol, and polish the substrate with sandpaper to increase the surface roughness of the metal substrate;

[0015] S2. Add MXene-Ni@C-ODD and a waterborne epoxy curing agent to waterborne epoxy resin and stir to prepare a waterborne epoxy resin coating of MXene-Ni@C-ODD, abbreviated as the MO coating;

[0016] S3. Magnetically regulate the MO coating during scraping with a coater to make MXene-Ni@C-ODD adhere to the waterborne epoxy resin coating. After curing at room temperature, a modified waterborne epoxy resin coating, abbreviated as the mMO coating, is prepared on the surface of the metal substrate.

[0017] Preferably, the metal substrate in step S1 is stainless steel, aluminum alloy, magnesium alloy, titanium alloy or copper alloy.

[0018] Preferably, the addition amount of MXene-Ni@C-ODD in step S2 is 0.001-20 wt.% of the waterborne epoxy resin; the waterborne epoxy resin is epoxy resin F0716, epoxy resin H1150 or epoxy resin H145, and the waterborne epoxy curing agent is F0716., H205B or H206B. The mass ratio of the waterborne epoxy resin to the waterborne epoxy curing agent is (1-10):1.

[0019] Preferably, the thickness of the mMO coating in step S3 is 10-100 μm.

[0020] The application of the described MXene-Ni@C-ODD in the field of metal surface protection.

[0021] Compared with the prior art, the present invention has the following beneficial effects:

[0022] 1. The MOFs of the present invention are formed by the coordination assembly of nickel ions and organic ligands. During hydrothermal treatment, MOFs and MOFs assembled on MXene are formed simultaneously, and after annealing, MXene-Ni@C is formed. MXene-Ni@C has magnetism and can load the corrosion inhibitor ODD to form a waterborne epoxy resin coating of MXene-Ni@C-ODD, and then it is regulated to obtain a modified waterborne epoxy resin coating. Due to the strong adhesion of the waterborne epoxy resin, this modified waterborne epoxy resin coating can be firmly combined with the metal substrate and is not easy to fall off. Adding MXene-Ni@C-ODD to the waterborne epoxy resin coating endows the waterborne epoxy resin coating with a stronger corrosion inhibition effect. Combining magnetic field regulation and scraping coating, this modified waterborne epoxy resin coating has physical shielding, self-healing performance and corrosion resistance, solves the problem that the waterborne epoxy resin coating is prone to cracking during curing, and avoids water and corrosive substances from contacting the substrate through the micropores formed during the easy cracking of the waterborne epoxy resin coating during curing to cause corrosion. At the same time, MXene-Ni@C-ODD is ultrasonically treated to make it more uniformly dispersed in the waterborne epoxy resin coating, achieving a good anti-corrosion effect. The performance of the modified waterborne epoxy resin coating after magnetic field regulation is more excellent, and the corrosion current reaches 5.2×10 -13 A·cm -2 or more.

[0023] 2. In the present invention, adding a suspension of the corrosion inhibitor hydrophilic heptadecenylaminoethylimidazoline quaternary ammonium salt to the waterborne epoxy resin coating plays a protective role on the waterborne epoxy resin coating. When the waterborne epoxy resin coating has defects due to changes in the external environment, the corrosion inhibitor plays a role and forms a precipitation layer and an adsorption layer on the surface of the metal substrate, so that the waterborne epoxy resin coating has self-healing ability, improves its anti-corrosion performance, and prolongs the service life of the substrate.

[0024] 3. The present invention conducts magnetic regulation on the waterborne epoxy resin coating of MXene-Ni@C-ODD, solves the problem that MXene in MXene-Ni@C-ODD is randomly distributed in the waterborne epoxy resin coating, enables MXene in MXene-Ni@C-ODD to be arranged parallel to the metal substrate, exerts its physical shielding effect, and improves the anti-corrosion effect of the waterborne epoxy resin coating. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 It is a schematic scanning electron microscope morphology diagram of MXene and MXene-Ni@C-ODD in Example 1.

[0026] Figure 2 It is a schematic diagram of the paramagnetism of MXene and MXene-Ni@C-ODD under a magnet in Example 1.

[0027] Figure 3The macroscopic morphology of the surface of the waterborne epoxy resin coating of MXene-Ni@C-ODD prepared in Example 1.

[0028] Figure 4 The impedance spectrograms of the waterborne epoxy resin coating of Example 1, the waterborne epoxy resin coating of MXene-Ni@C-ODD (MO coating), and the modified waterborne epoxy resin coating (mMO coating).

[0029] Figure 5 The Tafel test curves after scratching the coatings of the waterborne epoxy resin coating of Example 1, the waterborne epoxy resin coating of MXene-Ni@C-ODD (MO coating), and the modified waterborne epoxy resin coating (mMO coating). Detailed implementation manners

[0030] The present invention will be further described in detail below in conjunction with embodiments, but the implementation manners of the present invention are not limited thereto. Unless otherwise specified, the technical means used in the embodiments are conventional means well known to those skilled in the art. Unless otherwise specified, the reagents, methods, and equipment used in the present invention are conventional reagents, methods, and equipment in the technical field.

[0031] In the embodiments of the present invention, the waterborne epoxy resin F0716 and the curing agent F0716 are purchased from Shenzhen Yoshida Chemical Co., Ltd.; the waterborne epoxy resin H1150 and the curing agent H205B are purchased from Shanghai Hanzhong Chemical Co., Ltd.; the waterborne epoxy resin H145 and the curing agent H206B are purchased from Shanghai Hanzhong Coating Co., Ltd.

[0032] Example 1

[0033] 1. Pretreat the metal substrate Q235, degrease the substrate with acetone or absolute ethanol, and polish the substrate with sandpaper to increase the surface roughness of the substrate, so as to facilitate the attachment of the waterborne epoxy resin to the substrate;

[0034] 2. Mix NiCl2·6H2O and the organic ligand 2,3,6,7,10,11-hexahydroxytriphenylene hydrate (HHTP) with a mass ratio of 10:7, add them to DMF, dissolve them by ultrasonic wave at a power of 11 - 20 W / L, then add 40 mL of a 0.5 mg / mL ultrasonically dispersed MXene (Ti3C2T x , where x is the total number of surface functional groups of the material, x = 1 - 3) suspension, perform hydrothermal treatment at 80 °C for 10 h, precipitate, dry, and collect to prepare MOFs-MXene. After annealing treatment at 700 °C, MXene-Ni@C is obtained. Then add it to a 70 wt.% corrosion inhibitor hydrophilic heptadecenylamine ethyl imidazoline quaternary ammonium salt (ODD) solution, load the corrosion inhibitor ODD on MXene-Ni@C, precipitate, collect, and dry to obtain MXene-Ni@C-ODD, abbreviated as mMO;

[0035] 3. Add 1 wt.% of MXene-Ni@C-ODD to the waterborne epoxy resin F0716, and then add the waterborne epoxy curing agent F0716 and mix and stir to obtain a waterborne epoxy resin coating of MXene-Ni@C-ODD, abbreviated as the MO coating. Among them, the mass ratio of the waterborne epoxy resin F0716 to the waterborne epoxy curing agent F0716 is 3:1.

[0036] 4. When using a coater for scraping, perform magnetic regulation on it. Place two magnets adsorbed on the front end of the coater, with the same magnetic poles attracting each other. When scraping forward, the magnetic MXene-Ni@C-ODD will tend to be arranged in parallel due to the magnetic field force, reducing the forward resistance. During the process of advancing, the magnetic field gradually weakens, and finally MXene-Ni@C-ODD will adhere to the waterborne epoxy resin coating. After curing at room temperature, a modified waterborne epoxy resin coating is prepared on the surface of the metal matrix Q235, abbreviated as the mMO coating.

[0037] Figure 1 are the scanning electron microscope morphology photos of MXene and MXene-Ni@C-ODD in Example 1. From Figure 1 it can be seen that the circular particles on MXene are Ni@C, and the white attachment is the ODD corrosion inhibitor loaded on Ni@C, indicating that MXene-Ni@C-ODD has been successfully prepared. Figure 2 is the paramagnetic schematic diagram of MXene and MXene-Ni@C-ODD under a magnet in Example 1. Load MXene and MXene-Ni@C-ODD into two bottles respectively, and place a magnet close to the middle of the two bottles. From Figure 2 it can be observed that MXene still remains at the bottom of the bottle, while MXene-Ni@C-ODD is adsorbed on the bottle wall close to the magnet, indicating that the prepared MXene-Ni@C-ODD has paramagnetism. Figure 3 is the morphology of the surface of the waterborne epoxy resin coating of MXene-Ni@C-ODD prepared in Example 1. From Figure 3 it can be seen that the color distribution of the prepared waterborne epoxy resin coating of MXene-Ni@C-ODD is uniform, and there are no small black dots formed by the aggregation of MXene-Ni@C-ODD, indicating that MXene-Ni@C-ODD can be evenly dispersed in the waterborne epoxy resin. Figure 4 are the impedance spectrograms of the waterborne epoxy resin coating, the waterborne epoxy resin coating of MXene-Ni@C-ODD, and the modified waterborne epoxy resin coating in Example 1. From Figure 4It can be seen that the addition of MXene-Ni@C-ODD can reduce the corrosion rate of anions on the metal matrix Q235 in 3.5 wt.% NaCl solution, and the impedance arc increases to 3.48×10 6 Ω·cm -2 after magnetic field regulation, which proves that MXene in MXene-Ni@C-ODD can be adjusted to be arranged parallel to the matrix after magnetic field regulation, better exerting its physical shielding effect. Figure 5 Tafel test curves after scratching the coatings of the waterborne epoxy resin coating of Example 1, the waterborne epoxy resin coating of MXene-Ni@C-ODD (MO coating) and the modified waterborne epoxy resin coating (mMO coating). From Figure 5 it can be seen that from the Tafel test after scratching the coating, the waterborne epoxy resin coating loses its organic passivation protection ability after being damaged, and the anti-corrosion protection fails. The coating added with MXene-Ni@C-ODD can successfully repair the coating, and the corrosion current is 8.2×10 -12 A·cm -2 . It maintains its cathodic protection effect. The performance of the modified waterborne epoxy resin coating after magnetic field regulation is more excellent, and the corrosion current reaches 5.2×10 -13 A·cm -2 .

[0038] Example 2

[0039] 1. Pretreat the metal matrix AZ31, degrease the matrix AZ31 with acetone or absolute ethanol, and polish the matrix with sandpaper to increase the surface roughness of the matrix, so as to facilitate the attachment of the waterborne epoxy resin to the matrix;

[0040] 2. Mix NiSO4·6H2O and the organic ligand terephthalic acid with a mass ratio of 10:7, add them to DMF and dissolve them by ultrasonic wave at a power of 11 - 20 W / L, then add 50 mL of a 0.5 mg / mL ultrasonically dispersed MXene (Ta4C3T x , where x is the total number of surface functional groups of the material, x = 1 - 3) suspension, perform hydrothermal treatment at 120 °C for 10 h, precipitate and dry to prepare MOFs-MXene. After annealing treatment at 800 °C, MXene-Ni@C is obtained. Then add it to a 70 wt.% inhibitor hydrophilic heptadecenylamine ethylimidazoline quaternary ammonium salt (ODD) solution, load the inhibitor ODD on MXene-Ni@C, collect the precipitate and dry it to obtain MXene-Ni@C-ODD, abbreviated as mMO.

[0041] 3. MXene-Ni@C-ODD (1 wt.%) was added to waterborne epoxy resin H1150, followed by waterborne epoxy curing agent H205B, and the mixture was stirred to produce a waterborne epoxy coating of MXene-Ni@C-ODD (MO coating). The mass ratio of waterborne epoxy resin H1150 to waterborne epoxy curing agent H205B was 4:1.

[0042] 4. When using a coater for scraping, it is magnetically controlled. Two magnets are placed on the front end of the coater. The magnetic poles of the same name attract each other. When the coating moves forward, the magnetic MXene-Ni@C-ODD tends to be arranged in parallel due to the force of the magnetic field, reducing the forward resistance. During the movement, the magnetic field gradually weakens, and eventually the MXene-Ni@C-ODD will adhere to the water-based epoxy coating. After curing at room temperature, a modified water-based epoxy resin coating is prepared on the surface of the substrate, abbreviated as mMO coating.

[0043] The MXene-Ni@C-ODD of this embodiment has paramagnetism. The color distribution of the modified waterborne epoxy resin coating is uniform, and there are no small black spots caused by the segregation of MXene-Ni@C-ODD. This shows that MXene-Ni@C-ODD can be evenly dispersed in the waterborne epoxy resin. From the electrochemical test results, the addition of MXene-Ni@C-ODD can reduce the corrosion rate, and the impedance arc increases to 2.99×10 6 Ω·cm -2 , proving that magnetic field manipulation can adjust the MXene in MXene-Ni@C-ODD to be arranged parallel to the substrate, thus better exerting its physical shielding effect. The Tafel test results after scratching the coating show that the waterborne epoxy resin coating loses its organic passivation protection ability after damage, and its anti-corrosion protection fails. The waterborne epoxy resin coating with MXene-Ni@C-ODD can successfully repair the coating and maintain its cathodic protection (corrosion current 8.8×10 -12 A.cm -2 ), the performance of the modified waterborne epoxy resin coating after magnetic field regulation is even better after healing, with a corrosion current of 6.2×10 -13 A.cm -2 .

[0044] Example 3

[0045] 1. Pre-treat the metal substrate ZL101 by degreasing it with acetone or anhydrous ethanol and polishing it with sandpaper to increase the surface roughness of the substrate to facilitate the adhesion of water-based epoxy resin to the substrate;

[0046] 2. Ni(OAc)2·6H2O and the organic ligand 1,3,5-benzenetricarboxylic acid with a mass ratio of 1:1 were mixed and added to DMF, and ultrasonic dissolution was carried out at a power of 11 - 20 W / L. Then, 50 mL of a 0.5 mg / mL ultrasonically dispersed MXene (TiN3T x , where x is the total number of surface functional groups of the material, and x = 1 - 3) suspension was added, and hydrothermal treatment was carried out at 180 °C for 10 h. The precipitate was collected and dried to prepare MOFs-MXene. After annealing treatment at 800 °C, MXene-Ni@C was obtained. Then, it was added to a 70 wt.% inhibitor hydrophilic heptadecenylamine ethyl imidazoline quaternary ammonium salt (ODD) solution, and the inhibitor ODD was loaded on MXene-Ni@C. The precipitate was collected and dried to obtain MXene-Ni@C-ODD, abbreviated as mMO.

[0047] 3. 2 wt.% of MXene-Ni@C-ODD was added to the waterborne epoxy resin H145, and then the waterborne epoxy curing agent H206B was added and mixed and stirred to prepare a waterborne epoxy resin coating of MXene-Ni@C-ODD, abbreviated as the MO coating. Among them, the mass ratio of the waterborne epoxy resin H145 to the waterborne epoxy curing agent H206B is 2:1.

[0048] 4. During the scraping with a coater, magnetic regulation was carried out. Two magnets were placed and adsorbed at the front end of the coater, and the same-named magnetic poles attracted each other. When scraping forward, the magnetic MXene-Ni@C-ODD would tend to be arranged in parallel due to the action of the magnetic field, reducing the forward resistance. During the process, the magnetic field gradually weakened, and finally MXene-Ni@C-ODD would adhere to the waterborne epoxy coating. After curing at room temperature, a modified waterborne epoxy resin coating, abbreviated as the mMO coating, was prepared on the substrate surface.

[0049] The MXene-Ni@C-ODD in this example has paramagnetism. The color distribution of the prepared modified waterborne epoxy resin coating is uniform, and there are no small black dots formed by the segregation of MXene-Ni@C-ODD, indicating that MXene-Ni@C-ODD can be evenly dispersed in the waterborne epoxy resin. From the electrochemical test results, the addition of MXene-Ni@C-ODD can reduce the corrosion rate, and after magnetic field regulation, the impedance arc increases to 3.11×10 6 Ω·cm -2, it is proved that after magnetic field regulation, the MXene in MXene-Ni@C-ODD can be adjusted to be arranged parallel to the substrate, so as to better play its physical shielding role. From the Tafel test results after scratching the coating, the waterborne epoxy resin coating loses the organic passivation protection ability after being damaged, and the anti-corrosion protection fails. The waterborne epoxy resin coating added with MXene-Ni@C-ODD can successfully repair the coating and maintain its cathodic protection effect (corrosion current 7.8×10 -12 A·cm -2 ). The performance of the modified waterborne epoxy resin coating after magnetic field regulation and healing is more excellent, and the corrosion current reaches 6.6×10 -13 A·cm -2 .

[0050] Example 4

[0051] 1. Pretreat the metal substrate 304, degrease the substrate 304 with acetone or absolute ethanol, and polish the substrate with sandpaper to increase the surface roughness of the substrate, so as to facilitate the attachment of the waterborne epoxy resin to the substrate;

[0052] 2. Mix Ni(OAc)2·6H2O and the organic ligand 1,3,5-benzenetricarboxylic acid with a mass ratio of 1:1, add them to DMF, dissolve them by ultrasonic wave at a power of 11-20 W / L, and then add 50 mL of a 0.5 mg / mL ultrasonically dispersed MXene (V2CT x , x is the total number of surface functional groups of the material, x = 1-3) suspension, perform hydrothermal treatment at 180 °C for 10 h, collect the precipitate and dry it to prepare MOFs-MXene. After annealing treatment at 800 °C, MXene-Ni@C is obtained, and then it is added to a 70 wt.% inhibitor hydrophilic heptadecenylamine ethyl imidazoline quaternary ammonium salt (ODD) solution, and the inhibitor ODD is loaded on MXene-Ni@C. Collect the precipitate and dry it to obtain MXene-Ni@C-ODD, abbreviated as mMO.

[0053] 3. Add 1 wt.% of MXene-Ni@C-ODD to the waterborne epoxy resin F0716, and then add the waterborne epoxy curing agent F0716 and mix and stir to prepare a waterborne epoxy resin coating of MXene-Ni@C-ODD, abbreviated as MO coating. Among them, the mass ratio of the waterborne epoxy resin F0716 to the waterborne epoxy curing agent F0716 is 3:1.

[0054] 4. During the scraping process using a coater, magnetic regulation is carried out. Two magnets are placed and adsorbed at the front end of the coater. Like magnetic poles attract each other. When scraping forward, the magnetic MXene-Ni@C-ODD will tend to be arranged in parallel due to the magnetic field force, reducing the forward resistance. During the process of advancing, the magnetic field gradually weakens. Eventually, MXene-Ni@C-ODD will adhere to the waterborne epoxy coating. After curing at room temperature, a modified waterborne epoxy resin coating, abbreviated as mMO coating, is prepared on the substrate surface.

[0055] The MXene-Ni@C-ODD in this example has paramagnetism. The prepared modified waterborne epoxy resin coating has a uniform color distribution, and there are no small black dots formed by the aggregation of MXene-Ni@C-ODD, indicating that MXene-Ni@C-ODD can be evenly dispersed in the waterborne epoxy resin. From the results of electrochemical tests, the addition of MXene-Ni@C-ODD can reduce the corrosion rate, and after magnetic field regulation, the impedance arc increases to 2.99×10 6 Ω·cm -2 , proving that after magnetic field regulation, the MXene in MXene-Ni@C-ODD can be adjusted to be parallel to the substrate arrangement, better exerting its physical shielding effect. From the Tafel test results after scratching the coating, the waterborne epoxy resin coating loses its organic passivation protection ability after being damaged, and the anti-corrosion protection fails. The waterborne epoxy resin coating added with MXene-Ni@C-ODD can successfully repair the coating and maintain its cathodic protection effect (corrosion current 8.8×10 -12 A·cm -2 ). The performance of the modified waterborne epoxy resin coating after magnetic field regulation is more excellent after healing, and the corrosion current reaches 6.2×10 -13 A·cm -2 .

[0056] Due to the strong adhesion of waterborne epoxy resin, the prepared modified waterborne epoxy resin coating can be firmly bonded to the substrate and is not easily peeled off; moreover, the modified waterborne epoxy resin has a relatively high hardness, enhancing the wear resistance of the modified waterborne epoxy resin coating; the anti-corrosion requirement of the substrate is achieved by the method of preparing the modified waterborne epoxy resin coating, and this preparation process is relatively simple, with less equipment requirements and easy operation; adding MXene-Ni@C-ODD to the waterborne epoxy resin coating solves the problem that the waterborne epoxy resin coating is prone to cracking during the curing process, avoiding corrosion caused by water and corrosive substances contacting the substrate through the internal micropores formed by the cracking of the waterborne epoxy resin coating. At the same time, after ultrasonic treatment of MXene-Ni@C-ODD, the problem that MXene in MXene-Ni@C-ODD is prone to agglomeration can be solved, increasing its dispersibility in the waterborne epoxy resin coating, enabling MXene-Ni@C-ODD to be more evenly dispersed in the waterborne epoxy resin coating and playing a good anti-corrosion effect; adding a certain concentration of inhibitor ODD solution to the waterborne epoxy resin coating can protect the coating. When the waterborne epoxy resin coating has defects due to changes in the external environment, the inhibitor plays a role, forming a precipitation layer and an adsorption layer on the substrate surface, so that the waterborne epoxy resin coating has self-healing ability, improving its anti-corrosion performance and extending the service life of the substrate; magnetic regulation of MXene-Ni@C-ODD solves the problem that MXene in MXene-Ni@C-ODD is randomly distributed in the coating, enabling MXene in MXene-Ni@C-ODD to be arranged parallel to the substrate and exerting its physical shielding effect to enhance the anti-corrosion effect of the waterborne epoxy resin coating.

[0057] The waterborne epoxy resin coating of the present invention has excellent physical shielding and self-healing properties, which are due to the waterborne epoxy coating prepared by magnetic field orientation regulation of Ni@C-MXene on the substrate surface. The proportion of MXene determines the density of the waterborne epoxy coating, and insufficient MXene content affects the anti-corrosion effect and physical shielding effect of the coating. The proportion of MOFs determines the loading amount and release rate of the coating inhibitor, enabling it to be released when exposed. The parallel arrangement of MXene after magnetic field regulation provides more excellent physical shielding characteristics, enabling it to resist harsh corrosion environments such as:

[0058] The modified waterborne epoxy resin coating of the present invention can form a dense protective film on the metal surface, preventing water, oxygen and corrosive media from contacting the metal, and is widely used in the anti-corrosion of various metal products. For example, for outdoor metal billboards, when coated with the modified coating, it can resist the humid environment and acid rain erosion, and extend the service life. In the chemical industry, many metal equipment will come into contact with corrosive media such as acids, alkalis and salts. The modified waterborne epoxy resin coating can protect these equipment with excellent chemical corrosion resistance. For example, for the metal tank storing sulfuric acid, when the inner wall is coated with the modified coating, it can prevent the corrosion of the sulfuric acid to the tank body and ensure the safe operation of the equipment. Using this solution can form a flat, wear-resistant and stain-resistant coating on the ground of industrial plants, warehouses, parking lots and other places, meeting the use requirements of different places. For example, for the workshop floor of some electronics factories, using this coating can not only provide good wear resistance and corrosion resistance, but also has the characteristics of environmental protection, non-toxic and pollution-free, meeting the requirements of the electronics factory for the production environment. In food machinery, the modified waterborne epoxy resin coating enables food processing equipment to have good anti-wear and high-temperature resistance, so that the equipment can still maintain the structural stability when working at high temperature, reduce the wear rate during long-term operation, extend the service life of the equipment and reduce costs. In medical equipment, the modified waterborne epoxy resin coating can have a good anti-corrosion effect on the metal parts of the equipment, avoid the erosion of disinfectants, cleaning agents, etc. on the metal parts in the hospital, prevent the equipment from rusting, and facilitate cleaning and disinfection.

[0059] Due to the large specific surface area of MXene in magnetic MXene-Ni@C-ODD, it can fully load the corrosion inhibitor, just like a microcapsule wrapping the corrosion inhibitor, which can quickly capture the metal ions released during the initial stage of corrosion when the waterborne epoxy resin coating is broken, and form a new corrosion inhibition layer to achieve the self-healing function. The self-healing performance of the modified waterborne epoxy resin coating has been mainly applied in many fields, especially in scenarios that require long-term protection, anti-damage or are difficult to maintain. The following are its main application fields: In marine and ship engineering, such as offshore platforms, ship hulls, port facilities, the microcapsule wraps the corrosion inhibitor. After the coating is broken, the corresponding position releases the corrosion inhibition components, which are dispersed in the coating. When the coating is washed by sea waves or mechanically damaged, the capsule breaks and releases the corrosion inhibitor, which combines with metal ions to form a new slow-release layer at the crack to resist seawater corrosion.

[0060] All in all, the modified waterborne epoxy resin coating of the present invention comprehensively utilizes the characteristics of physical shielding and strong self-healing performance, further improves the corrosion resistance of the green organic coating, and enables it to be applied in various harsh corrosion environments for a longer time.

[0061] The above embodiments are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above embodiments. Any other changes, modifications, substitutions, combinations, and simplifications made without departing from the spirit and principle of the present invention shall be equivalent replacement methods and are all included in the protection scope of the present invention.

Claims

1. A MXene-Ni@C-ODD, characterized in that, The MXene-Ni@C-ODD is abbreviated as mMO, and the MXene-Ni@C-ODD is prepared by dissolving a nickel source and an organic ligand in a solvent, adding an MXene suspension, performing hydrothermal treatment at 80-180 °C, collecting the precipitate and drying to obtain MOFs-MXene, annealing at 200-800 °C to obtain MXene-Ni@C, and then adding MXene-Ni@C to a corrosion inhibitor solution of heptadecenylamine ethyl imidazoline quaternary ammonium salt, loading the corrosion inhibitor on MXene-Ni@C, and collecting the precipitate and drying.

2. The MXene-Ni@C-ODD according to claim 1, characterized in that, The nickel source is NiCl2·6H2O, Ni(NO3)2·6H2O, NiSO4·6H2O or Ni(OAc)2·4H2O, and the organic ligand is 2,3,6,7,10,11-hexahydroxy triphenylene hydrate, phthalic acid, terephthalic acid, 1,3,5-benzenetricarboxylic acid or TDC (thiophene-2,5-dicarboxylic acid) benzenetricarboxylic acid; the solvent is DMF, water or ethanol.

3. The MXene-Ni@C-ODD according to claim 1, wherein The mass ratio of the nickel source, the organic ligand and the solvent is (1-10):(1-10):(1-10); the mass ratio of MXene and MOFs in the MOFs-MXene is (1-10):(1-10); the mass ratio of MXene-Ni@C to heptadecenylamine ethyl imidazoline quaternary ammonium salt in the heptadecenylamine ethyl imidazoline quaternary ammonium salt solution is (1-10):

1.

4. The MXene-Ni@C-ODD according to claim 1, wherein The MXene is Ti3C2T x , Ta4C3T x , TiN3T x , V2CT x , Nb2CT x or Ti3CNT x , where x = 1 to 3; the concentration of the MXene suspension is 0.1 to 10 mg / mL; the concentration of the heptadecenylamine ethyl imidazoline quaternary ammonium salt solution is 1 to 100 wt.%.

5. A corrosion-resistant modified waterborne epoxy resin coating, characterized in that, The modified waterborne epoxy resin coating is prepared from the MXene-Ni@C-ODD according to any one of claims 1-4.

6. The preparation method of the corrosion-resistant modified waterborne epoxy resin coating according to claim 5, characterized in that, It includes the following steps; S1. Degrease the metal substrate with acetone or absolute ethanol, and polish the substrate with sandpaper to increase the surface roughness of the metal substrate; S2. Stir MXene-Ni@C-ODD and a waterborne epoxy curing agent into waterborne epoxy resin to prepare a waterborne epoxy resin coating of MXene-Ni@C-ODD, abbreviated as MO coating; S3. Magnetically regulate the MO coating during scraping with a coater to make MXene-Ni@C-ODD adhere to the waterborne epoxy resin coating, and after curing at room temperature, a modified waterborne epoxy resin coating, abbreviated as mMO coating, is prepared on the surface of the metal substrate.

7. The preparation method of the corrosion-resistant modified waterborne epoxy resin coating according to claim 6, characterized in that, The metal substrate in step S1 is stainless steel, aluminum alloy, magnesium alloy, titanium alloy or copper alloy.

8. The preparation method of the corrosion-resistant modified waterborne epoxy resin coating according to claim 6, characterized in that, In step S2, the addition amount of MXene-Ni@C-ODD is 0.001-20 wt.% of the waterborne epoxy resin; the waterborne epoxy resin is epoxy resin F0716, epoxy resin H1150 or epoxy resin H145, the waterborne epoxy curing agent is F0716., H205B or H206B, and the mass ratio of the waterborne epoxy resin and the waterborne epoxy curing agent is (1-10):

1.

9. The preparation method of the corrosion-resistant modified waterborne epoxy resin coating according to claim 6, characterized in that, The thickness of the mMO coating in step S3 is 10-100 μm.

10. Use of the MXene-Ni@C-ODD according to any one of claims 1-4 in the field of metal surface protection.

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