CN113637338B - Modified hexagonal boron nitride, water-based anti-oxidation anticorrosive coating and preparation method thereof - Google Patents
Modified hexagonal boron nitride, water-based anti-oxidation anticorrosive coating and preparation method thereof Download PDFInfo
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Abstract
The invention discloses modified hexagonal boron nitride, a water-based anti-oxidation anticorrosive coating and a preparation method thereof, wherein the modified hexagonal boron nitride is characterized by comprising functional carbon nano-particles; the functional carbon nano-particles are carbon nano-particles modified by a silane coupling agent; the carbon nano-particles are products of a hydrothermal synthesis reaction of citric acid and ethylenediamine; the water-based anti-oxidation anticorrosive coating comprises the modified hexagonal boron nitride; the problems that the existing hexagonal boron nitride is easy to agglomerate in a water-based resin matrix to influence the corrosion resistance of a water-based paint coating and the existing water-based anticorrosive paint has poor corrosion resistance due to poor shielding capability on a corrosive medium in a severe oxygen corrosion environment are solved.
Description
Technical Field
The disclosure relates to a functional filler, a water-based anticorrosive paint using the functional filler and a preparation method thereof.
Background
Oxygen is a strong depolarizer and can directly participate in the cathodic reduction reaction in the corrosion process to accelerate the cathodic reaction, and a higher oxygen partial pressure can further accelerate the cathodic reaction of corrosion. Therefore, the corrosion rate of metal equipment is improved by more than two orders of magnitude in an extreme oxygen environment, particularly in high-pressure and high-oxygen-content environments such as high-pressure air injection oil extraction, large-scale compressed air energy storage and the like. The preparation of the functional anticorrosive coating suitable for the severe oxygen corrosion environment is an important requirement and technical difficulty of China.
The water-based paint contains less toxic heavy metals and Volatile Organic Compounds (VOCs), is environment-friendly and harmless to human health, and therefore receives more and more attention. However, water-based coatings generally have problems of low degree of curing, poor degree of crosslinking, difficulty in film formation, poor adhesion to metal materials, and the like. And residual hydrophilic groups and surfactants in the water-based paint can form polar channels to accelerate the permeation of corrosive media, so that the shielding capability of the coating on the corrosive media is poor, especially in a severe oxygen corrosion environment.
Hexagonal boron nitride is a two-dimensional nano sheet material, has excellent barrier property, mechanical property and chemical inertness, and is often used for improving the compactness, the mechanical property and the barrier property to corrosive media of an aqueous coating. However, since the surface tension of water is greater than the critical wetting surface tension of hexagonal boron nitride, the aqueous resin hardly achieves high penetration and dispersion of hexagonal boron nitride, and thus hexagonal boron nitride easily agglomerates in the aqueous resin matrix and causes defects in the coating layer.
In addition, the traditional coating preparation process cannot regulate and control the arrangement mode of the hexagonal boron nitride, so that the hexagonal boron nitride is randomly arranged in the aqueous resin matrix, and the blocking capability of the hexagonal boron nitride cannot be maximized. Therefore, the hexagonal boron nitride can be stably dispersed in water for a long time, is well compatible with water-based resin, maximizes the barrier property of the hexagonal boron nitride, enables the corresponding coating to resist harsh oxygen corrosion environment, and is a research difficulty in the field of water-based coatings.
Disclosure of Invention
In view of the above, the present disclosure provides modified hexagonal boron nitride, which solves the problem that the existing hexagonal boron nitride is easy to agglomerate in an aqueous resin matrix, so as to affect the corrosion resistance of an aqueous coating.
In addition, the disclosure also provides a water-based anti-oxidation anticorrosive coating, which solves the problem that the existing water-based anticorrosive coating has poor anticorrosive performance due to poor shielding capability on corrosive media in a severe corrosion environment.
Meanwhile, the disclosure also provides a preparation method of the modified hexagonal boron nitride and the water-based antioxidant anticorrosive coating.
In a first aspect, the modified hexagonal boron nitride is characterized by comprising:
a functional carbon nanoparticle;
the functional carbon nano-particles are carbon nano-particles modified by a silane coupling agent;
the carbon nano-particles are products of a hydrothermal synthesis reaction of citric acid and ethylenediamine.
Further, the silane coupling agent is gamma-glycidoxypropyltrimethoxysilane;
and/or the presence of a gas in the interior of the container,
the hydrothermal synthesis reaction is carried out by the following raw materials in parts by weight:
5-15 parts of citric acid;
2-7 parts of ethylenediamine;
80-90 parts of water.
Further, the modification method comprises the following steps:
uniformly dispersing 0.1-0.5 part of the carbon nano-particles in a mixed solution of 10-20 parts of water and 80-90 parts of ethanol to obtain a first mixed solution;
uniformly dispersing 0.1-0.5 part of the silane coupling agent in the first mixed solution to obtain a second mixed solution;
filtering and freeze-drying the second mixed solution to obtain the functional carbon nano-particles with the particle size of 100-200 nm;
and/or the presence of a gas in the interior of the container,
the method for obtaining the product comprises the following steps:
uniformly mixing the citric acid, the ethylenediamine and water, and then carrying out the hydrothermal synthesis reaction at the temperature of 150-250 ℃ for 3-6 h to obtain a reactant;
filtering and freeze-drying the reaction to give the product having a particle size of 20-50 nm.
In a second aspect, the preparation method of modified hexagonal boron nitride is characterized by comprising the following steps:
the functional carbon nanoparticles of any one of claims 1-3;
uniformly dispersing the functional carbon nano particles and the hexagonal boron nitride in water to obtain a mixture;
and filtering and freeze-drying the mixture to obtain the modified hexagonal boron nitride.
Further, calculated according to the mass parts, the functional carbon nano particles are 1-5 parts, the hexagonal boron nitride is 3-10 parts, and the water is 85-95 parts.
In a third aspect, the water-based oxidation and corrosion resistant coating is made of a water-based oxidation and corrosion resistant coating, and is characterized in that the coating comprises:
the modified hexagonal boron nitride of the first aspect.
Further, the coating further comprises:
waterborne epoxy resin, a curing agent and water.
Further, 20-30 parts of the waterborne epoxy resin, 30-40 parts of the curing agent, 1-10 parts of the modified hexagonal boron nitride and 30-50 parts of water;
and/or the presence of a gas in the interior of the container,
the waterborne epoxy resin is modified bisphenol A epoxy resin;
the curing agent is an aliphatic polyamine curing agent.
In a fourth aspect, the preparation method of the water-based antioxidant anticorrosive coating is characterized by comprising the following steps:
the aqueous oxygen resistant corrosion resistant coating of any one of claims 6-8;
coating the water-based oxygen-resistant anticorrosive paint by using a spin-on orientation method to prepare the coating.
Further, the spin-on alignment method includes:
after the water-based oxygen-resistant anticorrosive paint is coated on the surface of a metal material, rotating at the rotating speed of 500-3000 rpm for 10-60 s;
and/or the presence of a gas in the atmosphere,
the coating is dried at 40-100 ℃ for 3-6 h.
Further, the rotation speed is 1500 rpm;
the rotation time was 40 s.
The invention has the following beneficial effects:
1. improving the dispersibility of hexagonal boron nitride
According to the modified hexagonal boron nitride disclosed by the invention, the modified carbon nanoparticles have various groups such as amino groups, carboxyl groups and hydroxyl groups, and the carbon nanoparticles are further modified by utilizing gamma-glycidyl ether oxypropyltrimethoxysilane to obtain functional carbon nanoparticles, so that epoxy and silanol groups are added on the surfaces of the functional carbon nanoparticles, thus the hexagonal boron nitride is modified by pi-pi action between the functional carbon nanoparticles and the hexagonal boron nitride, sufficient surface charges of the hexagonal boron nitride are given to overcome the effects of hydrophobic force and van der Waals force, and the problem of agglomeration caused by mismatching of surface energy between the hexagonal boron nitride and water is solved, and the modified hexagonal boron nitride nanosheet disclosed by the invention can be stably dispersed in water for more than 7 days;
2. improving the corrosion resistance of the water-based anticorrosive coating
1. Because the oxygen mass transfer rate and the oxygen mass transfer capacity in the high-pressure and high-oxygen-content environment are obviously improved, and the existence of the surface of the functional carbon nano-particles is beneficial to O 2 The adsorbed charged sites can promote the breakage of O-O bonds to generate active oxygen atoms with higher reactivity with carbon steel, and a compact passive film is generated on the surface of the steel plate covered by the coating, so that the steel plate can be further protected.
2. The surface of the modified hexagonal boron nitride has silanol groups, and the modified hexagonal boron nitride can react with hydroxyl on the surface of a metal material to generate Si-O-Me (Me represents the metal material), si-O-Si and hydrogen bonds, so that the interface combination between the coating and the metal material can be enhanced, and the adhesion of the coating to the metal material is enhanced.
3. The damaged area is automatically repaired by the action of chemical bonds, hydrogen bonds and van der Waals force between the modified hexagonal boron nitrides and the aqueous resin system.
4. The surface of the modified hexagonal boron nitride has amino, hydroxyl, carboxyl, epoxy, silanol and other polybasic groups, and chemical bonds and hydrogen bond effects exist between the modified hexagonal boron nitride and epoxy resin and a curing agent, so that the modified hexagonal boron nitride can participate in the curing process of water-based resin, the interface bonding between the filler and the resin is enhanced, and the curing degree and the crosslinking density of a coating are improved.
In conclusion, the modified hexagonal boron nitride composite coating disclosed by the invention achieves the purpose of improving the anticorrosion performance of the coating through the synergistic effect of forming a passivation protective film, providing a self-repairing function, enhancing the curing degree of the coating and increasing the adhesion to a metal material, and solves the problem that the anticorrosion performance is poor due to poor shielding capability of the existing water-based anticorrosive coating to a corrosive medium under a severe corrosion environment.
Drawings
The above and other objects, features and advantages of the present disclosure will become more apparent from the following description of embodiments of the present disclosure with reference to the accompanying drawings, in which:
fig. 1A, 1B, 1C are TEM images of carbon nanoparticles, functional carbon nanoparticles, modified hexagonal boron nitride, respectively; as shown in fig. 1A, the carbon nanoparticles are approximately 20-50 nm; as shown in fig. 1B, the functional carbon nanoparticles are approximately 100-200 nm.
FIGS. 2A, 2B, 2C are digital images of functional carbon nanoparticles, hexagonal boron nitride, modified hexagonal boron nitride dispersion (1 mg/ml), respectively, after 7 days in distilled water; it can be seen that the modified hexagonal boron nitride can be stably dispersed in distilled water for more than 7 days.
FIG. 3A is a cross-sectional SEM photograph of comparative example 1;
FIG. 3B is a cross-sectional SEM image of comparative example 2;
FIG. 3C is a cross-sectional SEM image of comparative example 3;
FIG. 3D is a cross-sectional SEM photograph of example 1;
as can be seen from fig. 3A, the pure waterborne epoxy coating has low curing degree and some defects, and the cross section of the coating becomes smoother and almost has no defects after the functional carbon nanoparticles are added (fig. 3B), so that the curing degree of the coating is remarkably improved; as can be seen in fig. 3C, unmodified commercial hexagonal boron nitride agglomerates severely, disorganizes, and causes numerous defects in the aqueous epoxy matrix; as can be seen from fig. 3D, the modified hexagonal boron nitride nanosheets have good dispersibility and compatibility in the aqueous epoxy resin matrix, the interfacial bonding with the resin is also significantly enhanced, and the modified hexagonal boron nitride nanosheets are arranged in a horizontal orientation, so that under the combined action of the enhanced interfacial bonding and the improved degree of alignment order, there are substantially no defects in the coating.
FIGS. 4A-4D are pure O at 3 MPa, respectively 2 SEM images of metal surfaces covered by comparative examples 1, 2, 3 and example 1 after 15 days soaking in a harsh oxygen environment in conjunction with 3.5 wt% NaCl solution;
as can be seen from FIGS. 4A-4D, pure O at 3 MPa 2 After 15 days of soaking in a harsh oxygen environment in synergy with 3.5 wt% NaCl solution, the metal surfaces covered by comparative examples 1 and 3 had a significant amount of corrosion products, and the metal surfaces covered by comparative example 2 and example 1 had a dense passivation film protection.
FIGS. 5A1-5D 2 are images under a microscope of samples prepared with scratches on a glass plate; wherein 5A1-5D1 are initial images after comparative examples 1-3 and example 1 were lacerated, and 5A2-5D2 are images after comparative examples 1-3 and example 1 were lacerated and immersed in distilled water for 3 hours;
as can be seen from fig. 5A1, 5A2, 5C1, 5C2, the scratched areas of comparative examples 1, 3 did not heal after 3 hours of immersion in distilled water, while as can be seen from fig. 5B1, 5B2, 5D1, 5D2, the scratched areas of comparative example 2 and example 1 did heal significantly after 3 hours of immersion in distilled water.
Detailed Description
The present disclosure is described below based on examples, but it is worth explaining that the present disclosure is not limited to these examples. In the following detailed description of the present disclosure, some specific details are set forth in detail. However, the present disclosure may be fully understood by those skilled in the art for those parts not described in detail.
Furthermore, those of ordinary skill in the art will appreciate that the drawings are provided solely for the purposes, features, and advantages of the present disclosure, and are not necessarily drawn to scale.
Also, unless the context clearly requires otherwise, throughout the description and the claims, the words "comprise", "comprising", and the like are to be construed in an inclusive sense as opposed to an exclusive or exhaustive sense; that is, the meaning of "includes but is not limited to".
Comparative example 1
1. Metal surface pretreatment:
polishing the metal surface by a sand blasting machine, then ultrasonically cleaning the metal surface by using a solvent to remove impurities such as grease, dust and the like on the surface, and drying the metal surface at 80 ℃.
2. Preparing a pure water epoxy coating:
adding 25 parts of waterborne CYDW-100 epoxy resin and 35 parts of CYDHD-220 curing agent into 40 parts of distilled water, obtaining uniformly dispersed waterborne epoxy coating by continuous ultrasonic and mechanical stirring, coating the waterborne epoxy coating on the surface of a metal material by using a spin-coating orientation method, rotating 40 s at 1500 rpm at a high speed, heating at 60 ℃ to 5 h, and curing to obtain the pure waterborne epoxy coating.
3. Measurement of Performance
(1) The coatings prepared above were subjected to adhesion testing.
(2) Coating prepared in the way of being carried out at 3 MPa of pure O 2 And 3.5 wt% NaCl solution for 15 days and tested for low frequency impedance modulus.
Comparative example 2
1. The metal surface pretreatment is the same as that of comparative example 1;
2. preparing functional carbon nano-particles:
(1) Dissolving 10 parts of citric acid and 5 parts of ethylenediamine in 85 parts of distilled water, magnetically stirring for 30 min, transferring to a hydrothermal reaction kettle, heating at 200 ℃ to react for 5 h, filtering the reacted solution, and freeze-drying to obtain the carbon nanoparticles.
(2) And (2) dispersing 0.2 part of carbon nano-particles into a mixed solution of 19.8 parts of water and 79.8 parts of ethanol, adding 0.2 part of gamma-glycidyl ether oxypropyl trimethoxy silane, stirring in a water bath at 80 ℃ for 18 h, filtering, and freeze-drying to obtain the functional carbon nano-particles.
3. Preparation of functional carbon nano-particle/water-based epoxy coating
Adding 3 parts of functional carbon nano-particles, 25 parts of waterborne CYDW-100 epoxy resin and 35 parts of CYDHD-220 curing agent into 37 parts of distilled water, obtaining uniformly dispersed waterborne epoxy coating by continuous ultrasonic and mechanical stirring, coating the waterborne epoxy coating on the surface of a metal material by using a spin-coating orientation method, rotating at 1500 rpm at a high speed to 40 s, heating at 60 ℃ to 5 h, and curing to obtain the functional carbon nano-particle composite waterborne epoxy coating.
4. And (5) performance measurement.
Comparative example 3
1. The metal surface pretreatment is the same as that of comparative example 1;
2. preparation of hexagonal boron nitride/waterborne epoxy coating:
adding 3 parts of hexagonal boron nitride, 25 parts of aqueous CYDW-100 epoxy resin and 35 parts of CYDHD-220 curing agent into 47 parts of distilled water, obtaining uniformly dispersed aqueous epoxy coating through continuous ultrasonic and mechanical stirring, coating the aqueous epoxy coating on the surface of metal by using a spin-coating orientation method, rotating at 1500 rpm at a high speed, heating at 60 ℃ after 40 s, heating at 5 h, and curing to obtain the hexagonal boron nitride composite aqueous epoxy coating.
3. And (5) performance measurement.
Example 1
1. The metal surface pretreatment is the same as that of comparative example 1;
2. preparing functional carbon nano-particles:
(1) 10 parts of citric acid and 5 parts of ethylenediamine are dissolved in 85 parts of distilled water, magnetically stirred for 30 min, transferred to a hydrothermal reaction kettle, and heated at 200 ℃ to react with 5 h. And then freeze-drying the reacted solution to obtain the carbon nano-particles.
(2) 0.2 part of carbon nano-particles are dispersed in a mixed solution of 19.8 parts of water and 79.8 parts of ethanol, 0.2 part of gamma-glycidoxypropyltrimethoxysilane is added, and the mixture is stirred in a water bath at 80 ℃ to be 18 h. And then freeze-drying to obtain the functional carbon nano-particles.
3. Preparation of modified hexagonal boron nitride nano sheet
(1) 2 parts of functional carbon nanoparticles and 8 parts of hexagonal boron nitride are dispersed in 90 parts of distilled water.
(2) And (3) stirring, performing ultrasonic treatment, performing suction filtration, freeze drying and the like on the mixture to obtain the modified hexagonal boron nitride nano sheet.
4. Preparation of modified hexagonal boron nitride/waterborne epoxy anticorrosive coating
Adding 3 parts of modified hexagonal boron nitride, 25 parts of aqueous CYDW-100 epoxy resin and 35 parts of CYDHD-220 curing agent into 47 parts of distilled water, obtaining uniformly dispersed aqueous epoxy anticorrosive paint by continuous ultrasonic and mechanical stirring, coating the aqueous epoxy anticorrosive paint on the surface of a metal material by using a spin-coating orientation method, rotating 40 s at 1500 rpm at a high speed, heating 5 h at 60 ℃ to cure the coating, and obtaining the modified hexagonal boron nitride composite aqueous epoxy anticorrosive coating.
5. And (5) performance measurement.
Test results
1. The example 1 and the comparative examples 1 to 3 were subjected to adhesion tests, and the results thereof are shown in the following table 1.
Table 1 results of adhesion test of comparative examples 1 to 3 and example 1
| Experimental groups | Adhesion (Unit: MPa) |
| Comparative example 1 | 0.45±0.05 |
| Comparative example 2 | 1.45±0.10 |
| Comparative example 3 | 1.31±0.08 |
| Example 1 | 4.02±0.15 |
The results from the analysis in table 1 are as follows:
as can be seen from the adhesion data of comparative example 1 and comparative example 2 in table 1 in conjunction with fig. 3A and 3B, the introduction of the functional carbon nanoparticles can improve the degree of curing of the coating layer and enhance the interfacial bonding between the filler and the aqueous resin due to the chemical and hydrogen bonding between the functional carbon nanoparticles and the aqueous resin matrix.
In addition, because chemical bonds and hydrogen bonds exist between silanol groups on the surface of the functional carbon nano particles and hydroxyl groups on the surface of the metal material, the interface combination between the coating and the metal material is enhanced.
From the comparison results of comparative example 1 and comparative example 3, it can be seen that hexagonal boron nitride has strong mechanical properties, which can enhance the mechanical stability of the coating as a whole. The adhesion of the example 1 is obviously higher than that of the comparative examples 2 and 3, and the results prove that the curing degree of the coating is obviously improved under the synergistic effect of the functional carbon nano particles and the hexagonal boron nitride, a compact cross-linked network is formed in the coating, a compact bonding network is formed at the interface of the coating and the metal material, and finally the adhesion of the water-based coating to the metal material is obviously enhanced.
2. The low frequency impedance modulus of example 1 and comparative examples 1 to 3 was tested and the results are shown in table 2 below.
TABLE 2 results of low frequency impedance modulus test of comparative examples 1-3 and example 1
| Experimental groups | Low frequency impedance modulus (unit: ohm cm) 2 ） |
| Comparative example 1 | 2.63×10 5 |
| Comparative example 2 | 1.15×10 9 |
| Comparative example 3 | 2.15×10 5 |
| Example 1 | 2.02×10 10 |
The results from the analysis in table 2 are as follows:
it is seen from the comparison results of comparative example 1 and comparative example 2 and the comparison of table 1, fig. 3A and 3B, and fig. 3C and 3D that the introduction of the functional carbon nanoparticles can improve the degree of curing of the coating, enhance the interfacial bonding between the filler/aqueous resin, the coating/metal material, impart self-healing properties to the coating, and form a dense passivation film on the surface of the material, so the low-frequency impedance modulus of comparative example 2 is significantly higher than that of comparative example 1.
As can be seen from the comparison results of comparative example 1 and comparative example 3 and table 1, fig. 3C, unmodified commercial hexagonal boron nitride has poor compatibility with aqueous resin, and is heavily agglomerated in aqueous resin, causing numerous coating defects, resulting in comparative example 3 having a low frequency impedance modulus comparable to that of comparative example 1.
Comparing the results of various aspects, it is known that the modified hexagonal boron nitride is well dispersed and oriented in the aqueous resin (fig. 3D), the interfacial bonding between the filler/aqueous resin and the coating/metal material is enhanced (fig. 3D, table 1), the coating curing degree is improved, the damaged area can be repaired automatically (fig. 5B2 and 5D 2), and a dense passivation film is formed on the coating surface (fig. 4B and 4D), and finally the low-frequency impedance modulus of example 1 is 5 orders of magnitude higher than that of comparative example 1 (table 2). The mechanism of formation of the passivation film is: in a harsh oxygen environment, the mass transfer rate and the mass transfer quantity of oxygen are both high and fast, and at the moment, the functional carbon nano-particles exert the catalytic property thereof, so that the permeated oxygen is catalytically decomposed into oxygen atoms to react with a metal material to generate a compact passive film.
In addition, the present disclosure performed physical property tests on the carbon nanoparticles, the functional carbon nanoparticles, and the modified hexagonal boron nitride in example 1, as specifically shown in fig. 1A to 1C, and fig. 2A to 2C. Wherein, fig. 1A, fig. 1B, fig. 1C are TEM images of carbon nanoparticles, functional carbon nanoparticles, modified hexagonal boron nitride, respectively; as shown in fig. 1A, the carbon nanoparticles are approximately 20-50 nm; as shown in fig. 1B, the functional carbon nanoparticles are approximately 100-200 nm. FIGS. 2A, 2B, 2C are digital images of functional carbon nanoparticles, hexagonal boron nitride, modified hexagonal boron nitride dispersion (1 mg/ml), respectively, after 7 days in distilled water; it can be seen that the modified hexagonal boron nitride can be stably dispersed in distilled water for more than 7 days.
Example 2
1. The metal surface pretreatment is the same as that of comparative example 1;
2. functional carbon nanoparticle preparation
(1) 10 parts of citric acid and 5 parts of ethylenediamine are dissolved in 85 parts of distilled water, magnetically stirred for 30 min, transferred to a hydrothermal reaction kettle, and heated at 200 ℃ to react with 5 h. And then freeze-drying the reacted solution to obtain the carbon nano-particles.
(2) 0.2 part of carbon nano-particles are dispersed in a mixed solution of 19.8 parts of water and 79.8 parts of ethanol, 0.2 part of gamma-glycidoxypropyltrimethoxysilane is added, and the mixture is stirred in a water bath at 80 ℃ to be 18 h. And then freeze-drying to obtain the functional carbon nano-particles.
3. Preparation of modified hexagonal boron nitride nano sheet
(1) 2 parts of functional carbon nanoparticles and 8 parts of hexagonal boron nitride are dispersed in 90 parts of distilled water.
(2) And (3) stirring, performing ultrasonic treatment, suction filtration, freeze drying and the like on the mixture to obtain the modified hexagonal boron nitride nano sheet.
4. Preparation of modified hexagonal boron nitride/waterborne epoxy anticorrosive coating
Adding 1 part of modified hexagonal boron nitride, 25 parts of waterborne CYDW-100 epoxy resin and 35 parts of curing agent into 45 parts of distilled water, obtaining uniformly dispersed waterborne epoxy anticorrosive paint by continuous ultrasonic and mechanical stirring, coating the waterborne epoxy anticorrosive paint on the surface of a metal material by using a spin-coating orientation method, rotating 40 s at 1500 rpm at a high speed, heating 5 h at 60 ℃ and curing to obtain the modified hexagonal boron nitride composite waterborne epoxy anticorrosive paint.
5. And (4) performance measurement. This example is pure O at 3 MPa 2 The impedance value after soaking in the harsh environment cooperated with 3.5 wt% NaCl solution for 15 days is 1.51 × 10 10 ohm cm 2 。
Example 3
1. The metal surface pretreatment is the same as that of comparative example 1;
2. functional carbon nanoparticle preparation
(1) 10 parts of citric acid and 5 parts of ethylenediamine are dissolved in 85 parts of distilled water, magnetically stirred for 30 min, transferred to a hydrothermal reaction kettle, and heated at 200 ℃ to react with 5 h. And then freeze-drying the reacted solution to obtain the carbon nano-particles.
(2) 0.2 part of carbon nano-particles is dispersed in a mixed solution of 19.8 parts of water and 79.8 parts of ethanol, 0.2 part of gamma-glycidoxypropyltrimethoxysilane is added, and the mixture is stirred in a water bath at 80 ℃ to form 18 h. And then freeze-drying to obtain the functional carbon nano-particles.
3. Preparation of modified hexagonal boron nitride nano sheet
(1) 2 parts of functional carbon nanoparticles and 8 parts of hexagonal boron nitride were dispersed in 90 parts of distilled water.
(2) And (3) stirring, performing ultrasonic treatment, suction filtration, freeze drying and the like on the mixture to obtain the modified hexagonal boron nitride nano sheet.
4. Preparation of modified hexagonal boron nitride/waterborne epoxy coating
Adding 5 parts of modified hexagonal boron nitride, 25 parts of waterborne CYDW-100 epoxy resin and 35 parts of CYDHD-220 curing agent into 45 parts of distilled water, obtaining uniformly dispersed waterborne epoxy anticorrosive paint by continuous ultrasonic and mechanical stirring, coating the waterborne epoxy anticorrosive paint on the surface of a metal material by using a spin-coating orientation method, rotating at 1500 rpm at a high speed of 40 s, heating at 60 ℃ to 5 h, and curing to obtain the modified hexagonal boron nitride composite waterborne epoxy anticorrosive paint.
5. And (4) performance measurement. This example is pure O at 3 MPa 2 The impedance value after soaking in the harsh environment cooperated with 3.5 wt% NaCl solution for 15 days is 3.47 x 10 10 ohm cm 2 。
Example 4
1. The metal surface pretreatment is the same as that of comparative example 1;
2. functional carbon nanoparticle preparation
(1) 10 parts of citric acid and 5 parts of ethylenediamine are dissolved in 85 parts of distilled water, magnetically stirred for 30 min, transferred to a hydrothermal reaction kettle, and heated at 200 ℃ to react with 5 h. And then freeze-drying the reacted solution to obtain the carbon nano-particles.
(2) 0.2 part of carbon nano-particles is dispersed in a mixed solution of 19.8 parts of water and 79.8 parts of ethanol, 0.2 part of gamma-glycidoxypropyltrimethoxysilane is added, and the mixture is stirred in a water bath at 80 ℃ to form 18 h. And then freeze-drying to obtain the functional carbon nano-particles.
3. Preparation of modified hexagonal boron nitride nano sheet
(1) 2 parts of functional carbon nanoparticles and 8 parts of hexagonal boron nitride are dispersed in 90 parts of distilled water.
(2) And (3) stirring, performing ultrasonic treatment, performing suction filtration, freeze drying and the like on the mixture to obtain the modified hexagonal boron nitride nano sheet.
4. Preparation of modified hexagonal boron nitride/waterborne epoxy coating
Adding 7 parts of modified hexagonal boron nitride, 25 parts of aqueous CYDW-100 epoxy resin and 35 parts of CYDHD-220 curing agent into 43 parts of distilled water, obtaining a uniformly dispersed aqueous epoxy anticorrosive coating by continuous ultrasonic and mechanical stirring, coating the aqueous epoxy anticorrosive coating on the surface of a metal material by using a spin-coating orientation method, rotating at 1500 rpm at a high speed by 40 s, heating at 60 ℃ by 5 h, and curing to obtain the modified hexagonal boron nitride composite aqueous epoxy anticorrosive coating.
5. And (5) performance measurement. This example is pure O at 3 MPa 2 The impedance value after soaking in the harsh environment cooperated with 3.5 wt% NaCl solution for 15 days is 2.52 x 10 10 ohm cm 2 。
Example 5
1. The metal surface pretreatment is the same as that of comparative example 1;
2. functional carbon nanoparticle preparation
(1) 10 parts of citric acid and 5 parts of ethylenediamine are dissolved in 85 parts of distilled water, magnetically stirred for 30 min, transferred to a hydrothermal reaction kettle, and heated at 200 ℃ to react with 5 h. And then freeze-drying the reacted solution to obtain the carbon nano-particles.
(2) 0.2 part of carbon nano-particles are dispersed in a mixed solution of 19.8 parts of water and 79.8 parts of ethanol, 0.2 part of gamma-glycidoxypropyltrimethoxysilane is added, and the mixture is stirred in a water bath at 80 ℃ to be 18 h. And then freeze-drying to obtain the functional carbon nano-particles.
3. Preparation of modified hexagonal boron nitride nano sheet
(1) 2 parts of functional carbon nanoparticles and 8 parts of hexagonal boron nitride are dispersed in 90 parts of distilled water.
(2) And (3) stirring, performing ultrasonic treatment, performing suction filtration, freeze drying and the like on the mixture to obtain the modified hexagonal boron nitride nano sheet.
4. Preparation of modified hexagonal boron nitride/waterborne epoxy coating
Adding 10 parts of modified hexagonal boron nitride, 25 parts of waterborne CYDW-100 epoxy resin and 35 parts of CYDHD-220 curing agent into 30 parts of distilled water, obtaining uniformly dispersed waterborne epoxy anticorrosive paint by continuous ultrasonic and mechanical stirring, coating the waterborne epoxy anticorrosive paint on the surface of a metal material by using a spin-coating orientation method, rotating at 1500 rpm at a high speed of 40 s, heating at 60 ℃ to 5 h, and curing to obtain the modified hexagonal boron nitride composite waterborne epoxy anticorrosive paint.
5. And (5) performance measurement. This example is pure O at 3 MPa 2 The impedance value after soaking in the harsh environment cooperated with 3.5 wt% NaCl solution for 15 days is 1.94 multiplied by 10 10 ohm cm 2 。
The above-mentioned embodiments are merely embodiments for expressing the disclosure, and the description thereof is more specific and detailed, but not construed as limiting the scope of the disclosure. It should be noted that, for those skilled in the art, various changes, substitutions of equivalents, improvements and the like can be made without departing from the spirit of the disclosure, and these are all within the scope of the disclosure. Therefore, the protection scope of the present disclosure should be subject to the appended claims.
Claims (10)
1. An aqueous antioxidant anticorrosive coating prepared from an aqueous oxygen-resistant anticorrosive coating, characterized in that the coating comprises:
modified hexagonal boron nitride;
the modified hexagonal boron nitride comprises:
a functional carbon nanoparticle;
the functional carbon nano-particles are carbon nano-particles modified by a silane coupling agent;
the carbon nano-particles are products of a hydrothermal synthesis reaction of citric acid and ethylenediamine;
the method for obtaining the product comprises the following steps:
uniformly mixing the citric acid, the ethylenediamine and water, and then carrying out the hydrothermal synthesis reaction at the temperature of 150-250 ℃ for 3-6 h to obtain a reactant;
filtering and freeze-drying the reactant to obtain the product having a particle size of 20-50 nm;
uniformly dispersing the functional carbon nano-particles and hexagonal boron nitride in water to obtain a mixture;
filtering and freeze-drying the mixture to obtain the modified hexagonal boron nitride;
the silane coupling agent is gamma-glycidoxypropyltrimethoxysilane.
2. The aqueous antioxidant corrosion protective coating according to claim 1, wherein:
the raw materials for carrying out the hydrothermal synthesis reaction comprise the following components in parts by weight:
5-15 parts of citric acid;
2-7 parts of ethylenediamine;
80-90 parts of water.
3. The aqueous antioxidant corrosion protective coating according to claim 2, characterized in that:
the method for modifying the carbon nano-particles by the silane coupling agent comprises the following steps:
uniformly dispersing 0.1-0.5 part of the carbon nano-particles in a mixed solution of 10-20 parts of water and 80-90 parts of ethanol to obtain a first mixed solution;
uniformly dispersing 0.1-0.5 part of the silane coupling agent in the first mixed solution to obtain a second mixed solution;
and filtering and freeze-drying the second mixed solution to obtain the functional carbon nano-particles with the particle size of 100-200 nm.
4. The aqueous antioxidant corrosion protective coating according to claim 3, wherein:
according to the mass portion, 1-5 parts of functional carbon nano particles, 3-10 parts of hexagonal boron nitride and 85-95 parts of water.
5. The aqueous antioxidant corrosion protective coating of claim 1, wherein the coating further comprises:
waterborne epoxy resin, a curing agent and water.
6. The aqueous antioxidant corrosion protective coating according to claim 5, wherein:
20-30 parts of waterborne epoxy resin, 30-40 parts of curing agent, 1-10 parts of modified hexagonal boron nitride and 30-50 parts of water.
7. The aqueous antioxidant corrosion protective coating according to claim 5, wherein:
the waterborne epoxy resin is modified bisphenol A epoxy resin;
the curing agent is an aliphatic polyamine curing agent.
8. A preparation method of a water-based antioxidant anticorrosive coating is characterized by comprising the following steps:
the aqueous oxygen resistant corrosion resistant coating of any one of claims 5-7;
coating the water-based oxygen-resistant anticorrosive paint by using a spin-on orientation method to prepare the coating.
9. The method for preparing the aqueous antioxidant anticorrosive coating according to claim 8, wherein the spin-on orientation method comprises:
after the water-based oxygen-resistant anticorrosive paint is coated on the surface of a metal material, the metal material is rotated at the rotating speed of 500-3000 rpm for 10-60 s.
10. The method for preparing the aqueous antioxidant anticorrosive coating according to claim 8, wherein the spin-on orientation method comprises:
the coatings were dried at 40-100 ℃ for 3-6 h.
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