CN115895394B - Interface passivation type heavy-duty anticorrosive powder coating and preparation method and application thereof - Google Patents
Interface passivation type heavy-duty anticorrosive powder coating and preparation method and application thereof Download PDFInfo
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- CN115895394B CN115895394B CN202310029880.4A CN202310029880A CN115895394B CN 115895394 B CN115895394 B CN 115895394B CN 202310029880 A CN202310029880 A CN 202310029880A CN 115895394 B CN115895394 B CN 115895394B
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
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- 239000012621 metal-organic framework Substances 0.000 claims abstract description 38
- 239000002135 nanosheet Substances 0.000 claims abstract description 38
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- 239000011259 mixed solution Substances 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
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- QTRSWYWKHYAKEO-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-henicosafluorodecyl-tris(1,1,2,2,2-pentafluoroethoxy)silane Chemical compound FC(F)(F)C(F)(F)O[Si](OC(F)(F)C(F)(F)F)(OC(F)(F)C(F)(F)F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F QTRSWYWKHYAKEO-UHFFFAOYSA-N 0.000 claims 1
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Abstract
The invention discloses an interface passivation type heavy-duty powder coating and a preparation method and application thereof, and solves the problems of poor wet binding force and poor long-acting corrosion resistance of a metal matrix/coating interface in the existing heavy-duty coating technology. The coating comprises ethane-1, 1-bis (4-phenylcyanate), surface modified graphite alkyne, MOF (metal organic framework) @ MXene (transition metal carbo/nitride), filler and the like. The preparation method of the MOF@MXene comprises the following steps: and (3) growing central atoms (cobalt and nickel) on the surface of the MXene nano-sheet, wherein the ligand is MOF of tetrathiafulvalene-tetrabenzoic acid. The lamellar structure of graphite alkyne and MOF@MXene and passivation property thereof synergistically improve the corrosion resistance of the metal matrix. The interface passivation type heavy-duty powder coating can be applied to the fields of equipment protection in heavy-duty environments with high temperature and strong permeability in the fields of ocean, petrochemical industry, electric power, metallurgy, military industry and the like.
Description
Technical Field
The invention relates to a development technology of a protective material in a heavy corrosion environment, in particular to an interface passivation type heavy corrosion protection powder coating and a preparation method and application thereof.
Background
The high-temperature acid liquid/steam, high-temperature salt water and high-temperature corrosive water in petroleum drilling, refining, chemical industry, nuclear power, thermal power, environmental protection, ocean and other industries are easy to cause corrosion damage of the anti-corrosive materials, and cause great harm to the safe operation of production equipment. Conventional epoxy, organosilicon, phenolic paint, etc. are degraded and destroyed in such heavy corrosive environments in a relatively short time, gradually losing adhesion with metal, resulting in failure of the coating protection.
Disclosure of Invention
The invention aims to provide an interface passivation type heavy-duty anticorrosive powder coating and a preparation method thereof, which solve the difficult problem of effective protection of corrosive media with higher temperature and high permeability in the prior art.
The technical scheme of the invention is as follows:
an interface passivation type heavy-duty anticorrosive powder coating comprises the following components in parts by weight:
ethane-1, 1-bis (4-phenylcyanate): 30.0 to 50.0 parts;
phenolic modified epoxy resin: 10.0 to 20.0 parts;
surface fluorosilane modified graphite alkyne nanoplatelets: 2.0 to 5.0 parts;
mof@mxene:5.0 to 15.0 parts;
glass flakes: 10.0 to 20.0 parts;
the MOF@MXene is an MXene nano-sheet material with a metal-organic framework material containing cobalt and nickel grown on the surface.
Optionally, the epoxy equivalent of the phenolic aldehyde modified epoxy resin is 180 g/eq-300 g/eq;
optionally, the phenolic modified epoxy resin is NPCN-70.
Optionally, the number of layers of the surface fluorosilane modified graphite alkyne nano sheet is less than or equal to 10.
Optionally, the interface passivation type heavy-duty powder coating further comprises:
leveling agent: 0.5 to 1.5 parts;
defoaming agent: 0.5 to 1.5 portions.
The application also provides a preparation method of the interface passivation type heavy-duty anticorrosive powder coating, which comprises the following steps:
step one), preparing a surface fluorosilane modified graphite alkyne nano sheet: adding a perfluorodecyl triethoxysilane ethanol solution with the concentration of 2-4wt% into an acetic acid aqueous solution with the pH value of 4-5 to obtain a mixed solution, wherein the mass ratio of the fluorosilane ethanol solution to the acetic acid aqueous solution is 1:3 to 4; adding the graphite alkyne nano-sheets into a mixed solution to react to obtain the surface fluorosilane modified graphite alkyne nano-sheets, wherein the mass ratio of the graphite alkyne nano-sheets to the fluorosilane is 1: 1-1.5;
step two) preparing MOF@MXene: etching Ti by hydrofluoric acid 3 AlCN and ultrasonic stripping to obtain an MXene nano-sheet; mixing Co salt, ni salt and tetrathiafulvalene-tetrabenzoic acid ligand with the MXene nano-sheet, and reacting by an in-situ hydrothermal method to obtain the MXene nano-sheet material with the surface grown with a metal-organic framework material containing cobalt and nickel;
and thirdly), weighing raw materials of each component, adding the raw materials into a double-screw extruder, and crushing and screening the raw materials after melt extrusion to obtain the powder coating.
Optionally, adding graphite alkyne nano-sheets into the mixed solution in the step one), and stirring for 2-4 hours at 40-60 ℃; then centrifuging, and cleaning for 1-3 times by using absolute ethyl alcohol; heating in a vacuum furnace at 50-70 deg.c for 24-36 hr; grinding the mixture by using a mortar after heating is finished, and obtaining the surface fluorosilane modified graphite alkyne nanosheet powder.
Optionally, in the second step), the molar ratio of the Co salt, the Ni salt and the tetrathiafulvalene-tetrabenzoic acid ligand is 1-1.5: 1-1.5: 8-12 parts;
the reaction condition of the hydrothermal method reaction is that the reaction is carried out for 6-24 hours at the temperature of 100-150 ℃;
the mass ratio of the MXene nano-sheets in the MOF@MXene to the metal organic framework material containing cobalt and nickel is 1:0.2 to 0.8.
Optionally, the raw materials of the components in the step three) are added into a double-screw extruder, are extruded after being melted and mixed at 130-150 ℃, and are crushed and sieved to obtain the coating powder with the particle size of 30-40 mu m.
The application also provides the application of the interface passivation type heavy-duty anticorrosive powder coating.
Optionally, preheating a metal matrix in an oven at 50-70 ℃ for 20-30 min, then carrying out electrostatic spraying on the interface passivation type heavy anti-corrosion powder coating layer, then baking at 180-200 ℃ for 20-30 min, taking out, and naturally cooling to room temperature to obtain the interface passivation type heavy anti-corrosion powder coating.
Optionally, the metal matrix is carbon steel, aluminum, magnesium alloy, etc.
The graphite alkyne and the MOF@MXene in the formula coating have catalytic performance, and can catalyze the low-temperature curing of the cyanate resin when being heated and baked at 180-200 ℃; secondly, graphite alkyne and MOF@MXene have conductivity, and can passivate a contacted metal matrix during heating and baking to form a layer of compact oxide film, so that the corrosion resistance of metal is further improved; in addition, the graphite alkyne has good NaCl filtering capacity and can effectively prevent Cl - Penetration in the coating; finally, both the graphite alkyne and the MOF@MXene are two-dimensional structures, inThe labyrinth network can be formed in the coating, the diffusion path of the corrosive medium is prolonged, and the corrosion resistance of the coating is improved.
One specific embodiment employed in this application is as follows:
preparing fluorosilane modified surface modified graphite alkyne nano-sheet powder: the graphite alkyne nano sheet is less than or equal to 3 layers of graphite alkyne nano sheets or 5-10 layers of multilayer graphite alkyne nano sheets, and the surface modification process of the surface modified graphite alkyne nano sheet is as follows: adjusting the pH value of deionized water to 4-5 by adopting acetic acid to form an acetic acid solution, preparing a perfluorodecyl triethoxysilane ethanol solution with the concentration of 2-4wt%, taking a fluorosilane ethanol solution accounting for 1/4-1/3 of the acetic acid solution, adding the fluorosilane ethanol solution into the acetic acid solution, and stirring for 30-40 min at room temperature; adding graphite alkyne nano-sheets, and stirring for 2-4 hours at 40-60 ℃; centrifuging, washing with absolute ethyl alcohol for 1-3 times, and heating in a vacuum furnace at 50-70 ℃ for 24-36 h; grinding with a mortar to obtain the fluorosilane modified surface modified graphite alkyne nanosheet powder.
The MOF consists of Co and Ni bimetallic center atoms and tetrathiafulvalene-tetrabenzoic acid ligands; MXene is Ti 3 CNT x A nano-sheet. The preparation process is as follows: etching Ti by hydrofluoric acid 3 AlCN is ultrasonically stripped to obtain Ti as the component 3 CNT x Is a MXene nanoplatelet. And then mixing Co salt, ni salt and tetrathiafulvalene-tetrabenzoic acid ligand with the MXene nanosheets, and growing CN-MOF (MOF containing cobalt and nickel) on the surface of the MXene by an in-situ hydrothermal method to obtain the MOF@MXene core-shell structure material.
The preparation method of the interface passivation type heavy-duty powder coating comprises the following specific steps:
(1) Preparing powder: ethane-1, 1-bis (4-phenylcyanate) is used for preparing the catalyst by weight: 50.0 to 70.0 portions of surface modified graphite alkyne: 2.0 to 5.0 parts of MOF@MXene:5.0 to 15.0 portions of glass flake: 10.0 to 20.0 portions of flatting agent: 0.5-1.5 parts of defoamer: adding 0.5-1.5 parts into a double screw extruder, melting and mixing at 130-150 ℃ and extruding, crushing and screening to obtain the coating powder with the particle size of 30-40 mu m.
(2) The preparation of the coating comprises the steps of firstly preheating a metal matrix in a baking oven for 20-30 min at 50-70 ℃, then carrying out electrostatic spraying on powder, placing a sample plate in the baking oven, baking for 20-30 min at 180-200 ℃, taking out, and naturally cooling to room temperature to obtain the interface passivation type heavy anti-corrosion powder coating.
The design idea of the invention is as follows:
(1) Different from the traditional physical shielding mode of the coating, the invention adds special materials (graphite alkyne and MOF@MXene) with catalysis and conductivity into the coating, and when the coating is heated, the filler can passivate the metal matrix after contacting with the metal matrix to form a compact oxide layer so as to prevent corrosion of metal.
(2) The graphite alkyne has high filtering effect on NaCl and can prevent or delay the diffusion of corrosive medium, such as salt fog, in the coating.
(3) The graphite alkyne, MOF@MXene and other fillers have catalytic performance, and can reduce the curing activation energy of cyanate, so that the cyanate is crosslinked and cured at 180-200 ℃, and the triazine ring crosslinked network of the cyanate and the lamellar structures of the graphite alkyne and the MOF@MXene form a labyrinth-shaped physical shielding network in the coating, so that the penetration of corrosive media is further prevented. The coating is a passivation type corrosion-resistant coating, and has good high-temperature acid corrosion resistance, bonding strength, chemical damage resistance, radiation resistance and the like. The interface passivation type heavy-duty powder coating plays an important role in the industrial field, and the novel composite coating which has catalytic performance, passivates metal interfaces, forms a labyrinth-shaped physical crosslinking network and other functions and improves the corrosion resistance of the coating is not reported.
The invention has the advantages and beneficial effects as follows:
1. the coating of the present invention is a powder coating that does not produce VOC emissions compared to aqueous or oily coatings.
2. The interface passivation type heavy corrosion protection powder coating which can be used in a heavy corrosive environment at a higher temperature for a long time is prepared, and has the advantages of heavy corrosion resistance, high impermeability, temperature change resistance and the like.
3. The invention designs a metal surface passivation strategy, and the passivation of a metal matrix in the heating process is realized through the high electron mobility of the special conductive composite material, so that the overall corrosion resistance is improved.
4. The graphite alkyne filler in the invention can effectively filter NaCl and prevent the Cl from being contained - Is used for the penetration of corrosive medium in the coating.
5. The metal passivating agent used in the invention is a MOF@MXene two-dimensional material, and forms a compact labyrinth-shaped cross-linked network with the triazine ring structure of the cyanate resin, so that penetration of corrosive medium in the coating is further prevented.
Drawings
Fig. 1 is XRD patterns of example 1 and comparative example 1.
Detailed Description
Example 1
(1) In the embodiment, the interface passivation type heavy-duty powder coating comprises the following specific formula in parts by weight:
ethane-1, 1-bis (4-phenylcyanate): 50.0 parts;
phenolic modified epoxy resin: 10.0 parts;
surface modified graphite alkyne: 4.0 parts;
mof@mxene:10.0 parts;
glass flakes: 15.0 parts;
leveling agent (reseflow PV 88): 1.0 parts;
defoamer (BYK 961): 1.0 parts;
(2) The surface modification process of the surface modified graphite alkyne nano sheet is as follows: adjusting the pH value of deionized water to 4.5 by adopting acetic acid to form an acetic acid solution, preparing a perfluorodecyl triethoxysilane ethanol solution with the concentration of 3wt%, taking a fluorosilane ethanol solution accounting for 1/4 of the weight of the acetic acid solution, adding the fluorosilane ethanol solution into the acetic acid solution, and stirring at room temperature for 40min; adding graphite alkyne nano-sheets, and stirring for 3 hours at 50 ℃; centrifuging, washing with absolute ethanol for 3 times, and heating in a vacuum furnace at 70deg.C for 24 hr; grinding with a mortar to obtain the fluorosilane modified surface modified graphite alkyne nanosheet powder.
(3) The preparation process of MOF@MXene is as follows: etching Ti by hydrofluoric acid 3 AlCN is removed by ultrasonic wave to obtain Ti 3 CNT x MXeneA nano-sheet. After which Co salt (CoCl) 2 ) 1.3 parts of Ni salt (nickel chloride) 1.3 parts and 55.0 parts of tetrathiafulvalene-tetrabenzoic acid ligand are mixed with 115.0 parts of MXene nano-sheet, and CN-MOF is grown on the surface of MXene by an in-situ hydrothermal method (140 ℃ C., 9 h), so as to obtain the MOF@MXene filler.
(4) Preparing powder: ethane-1, 1-bis (4-phenylcyanate) is used for preparing the catalyst by weight: 60.0 parts of phenolic modified epoxy resin: 10.0 parts of surface-modified graphite alkyne: 4.0 parts of MOF@MXene:10.0 parts of glass flake: 15.0 parts of flatting agent: 1.0 parts of defoamer: 1.0 part of the powder is added into a double-screw extruder, and is extruded after being melted and mixed at 140 ℃, and the powder is crushed and sieved to obtain the coating powder with the particle size of 35 mu m.
(5) Firstly, preheating a metal matrix in a baking oven for 30min at 50-70 ℃, then, carrying out electrostatic spraying on four layers of powder, placing a sample plate in the baking oven, baking for 20min at 180 ℃, taking out, and naturally cooling to room temperature to obtain the interface passivation type heavy anti-corrosion powder coating.
Example 2
In this example, the surface modified graphite alkyne mass in the coating of example 1 was changed to 2.0 parts, the MOF@MXene mass was changed to 5.0 parts, and the other parameters were unchanged.
Example 3
In this example, the surface modified graphite alkyne mass in the coating of example 1 was changed to 5.0 parts, the MOF@MXene mass was changed to 15.0 parts, and the other parameters were unchanged.
Comparative example 1
In this comparative example, the coating of example 1 was not added with surface modified graphite alkyne and mof@mxene, and the other parameters were not changed.
Comparative example 2
In this comparative example, no surface-modified graphite alkyne was added to the coating of example 1, and the other parameters were unchanged.
Comparative example 3
In this comparative example, the coating of example 1 was not added mof@mxene, and the other parameters were not changed.
Data analysis: the thickness of the interface passivation type heavy-duty powder coating is 0.15mm. First we characterized the interface passivation effect of this interface passivation type heavy-duty powder coating, and tested the X-ray diffraction (XRD) patterns of example 1 and comparative example 1, and the results are shown in fig. 1.
As can be seen from fig. 1, the XRD peak positions of Fe/comparative example 1 and the Fe matrix are the same, and there is no excessive peak, indicating that comparative example 1 does not passivate the Fe matrix; while Fe/example 1 shows a crystalline peak of Fe2O3 around 33 °, indicating that example 1 passivated Fe; cu/example 1 shows a crystalline peak of pure copper, and the coating of example 1 has no passivation ability to the copper matrix, and the coating of example 1 can passivate active metals such as iron and aluminum.
After subjecting examples 1-3 and comparative examples 2-3 to the following corrosion treatments, the electrochemical impedance spectra and mechanical properties were tested:
(1) Soaking in 5wt% sulfuric acid solution at 90 deg.c for 1200 hr;
(2) Soaking in 3.5wt% saline water at 60 ℃ for 1320h;
(3) Soaking in a mixed solution of 3% hydrochloric acid and 1% hydrofluoric acid at 120deg.C for 720 hr.
Table 1 examples 1-3 electrochemical low frequency impedance and bond strength comparisons
From the comparative data in Table 1, it can be seen that the surface modified graphite alkyne of example 1 is the most appropriate amount with MOF@MXene; when the amount of the two is small, the coating cannot play a sufficient passivation effect and physical barrier property, and the corrosion resistance of the coating is weaker than that of the coating of the embodiment 1; when the equivalent weight is too high, dispersion in the coating is affected, and the corrosion resistance of the coating is lowered.
Table 2 comparison of electrochemical low frequency impedance and bond strength for example 1 and comparative examples 2-3
From the results in table 2, it can be seen that: (1) The surface modified graphite alkyne in the coating has better protective effect on the corrosion medium containing Cl < - >, and when the surface modified graphite alkyne is not added in the coating, the coating performance is obviously reduced in a saline environment. (2) The MOF@MXene in the coating has better corrosion protection effect on acid, and when the MOF@MXene is not added in the coating, the performance of the coating in acid liquor is obviously reduced.
In summary, the results of examples and comparative examples show that the interface passivation type heavy anti-corrosion powder coating provided by the invention has strong corrosion resistance, high permeation resistance, mechanical damage resistance and the like, and can be applied to the fields of high temperature and heavy corrosion production equipment protection and the like in the industrial field.
The foregoing description is only a few examples of the present application and is not intended to limit the present application in any way, and although the present application is disclosed in the preferred examples, it is not intended to limit the present application, and any person skilled in the art may make some changes or modifications to the disclosed technology without departing from the scope of the technical solution of the present application, and the technical solution is equivalent to the equivalent embodiments.
Claims (9)
1. The interface passivation type heavy-duty anticorrosive powder coating is characterized by comprising the following components in parts by weight:
ethane-1, 1-bis (4-phenylcyanate): 30.0 to 50.0 parts;
phenolic modified epoxy resin: 10.0 to 20.0 parts;
surface fluorosilane modified graphite alkyne nanoplatelets: 2.0 to 5.0 parts;
mof@mxene:5.0 to 15.0 parts;
glass flakes: 10.0 to 20.0 parts;
the number of layers of the surface fluorosilane modified graphite alkyne nano sheet is less than or equal to 10;
the MOF@MXene is an MXene nano-sheet material with a metal organic framework material containing cobalt and nickel grown on the surface.
2. The interface passivation type heavy-duty powder coating of claim 1, wherein the phenolic modified epoxy resin has an epoxy equivalent of 180g/eq to 300g/eq.
3. The interface passivation type heavy-duty powder coating according to claim 1, further comprising
Leveling agent: 0.5 to 1.5 parts;
defoaming agent: 0.5 to 1.5 portions.
4. The preparation method of the interface passivation type heavy-duty powder coating according to any one of claims 1 to 3, which is characterized by comprising the following steps:
step one), preparing a surface fluorosilane modified graphite alkyne nano sheet: adding a perfluorodecyl triethoxysilane ethanol solution with the concentration of 2-4wt% into an acetic acid aqueous solution with the pH value of 4-5 to obtain a mixed solution, wherein the mass ratio of the fluorosilane ethanol solution to the acetic acid aqueous solution is 1:3 to 4; adding a graphite alkyne nano-sheet into a mixed solution to react to obtain a surface fluorosilane modified graphite alkyne nano-sheet, wherein the mass ratio of the graphite alkyne nano-sheet to perfluorodecyl triethoxysilane is 1: 1-1.5;
step two) preparing MOF@MXene: etching Ti by hydrofluoric acid 3 AlCN and ultrasonic stripping to obtain an MXene nano-sheet; mixing Co salt, ni salt and tetrathiafulvalene-tetrabenzoic acid ligand with the MXene nano-sheet, and reacting by an in-situ hydrothermal method to obtain the MXene nano-sheet material with the surface grown with a metal-organic framework material containing cobalt and nickel;
and thirdly), weighing raw materials of each component, adding the raw materials into a double-screw extruder, and crushing and screening the raw materials after melt extrusion to obtain the powder coating.
5. The preparation method according to claim 4, wherein in the step one), after adding the graphite alkyne nanoplatelets into the mixed solution, stirring is carried out for 2-4 hours at 40-60 ℃; then centrifuging, and cleaning for 1-3 times by using absolute ethyl alcohol; heating in a vacuum furnace at 50-70 deg.c for 24-36 hr; grinding the mixture by using a mortar after heating is finished, and obtaining the surface fluorosilane modified graphite alkyne nanosheet powder.
6. The method according to claim 4, wherein in the second step), the molar ratio of the Co salt, the Ni salt and the tetrathiafulvalene-tetrabenzoic acid ligand is 1 to 1.5: 1-1.5: 8-12 parts;
the reaction condition of the hydrothermal method reaction is that the reaction is carried out for 6-24 hours at the temperature of 100-150 ℃;
the mass ratio of the MXene nano-sheets in the MOF@MXene to the metal organic framework material containing cobalt and nickel is 1:0.2 to 0.8.
7. The preparation method according to claim 4, wherein the raw materials of the components in the third step are added into a double-screw extruder, are extruded after being melted and mixed at 130-150 ℃, and are crushed and sieved to obtain the coating powder with the particle size of 30-40 μm.
8. The interface passivation type heavy-duty powder coating according to any one of claims 1 to 3 and the application of the interface passivation type heavy-duty powder coating obtained by the preparation method according to any one of claims 4 to 7 in the preparation of an anti-corrosion coating.
9. The use according to claim 8, wherein the metal substrate is preheated in an oven at 50-70 ℃ for 20-30 min, then the interface passivation type heavy anti-corrosion powder coating is sprayed electrostatically, then baked at 180-200 ℃ for 20-30 min, and taken out and naturally cooled to room temperature, thus obtaining the interface passivation type heavy anti-corrosion powder coating.
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| PCT/CN2023/139665 WO2024149031A1 (en) | 2023-01-09 | 2023-12-18 | Heat-conducting wave-absorbing auxiliary agent, low-temperature curing coating, heavy corrosion-resistant coating, and preparation method therefor and use thereof |
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