CN113004736A - Preparation method of modified boron nitride nanosheet and application of modified boron nitride nanosheet in improving corrosion resistance of aqueous organic protective coating - Google Patents
Preparation method of modified boron nitride nanosheet and application of modified boron nitride nanosheet in improving corrosion resistance of aqueous organic protective coating Download PDFInfo
- Publication number
- CN113004736A CN113004736A CN202110254885.8A CN202110254885A CN113004736A CN 113004736 A CN113004736 A CN 113004736A CN 202110254885 A CN202110254885 A CN 202110254885A CN 113004736 A CN113004736 A CN 113004736A
- Authority
- CN
- China
- Prior art keywords
- boron nitride
- nitride nanosheet
- nanosheet
- modified boron
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
Abstract
The invention belongs to the technical field of metal corrosion protection, and particularly relates to a preparation method of a modified boron nitride nanosheet and application thereof in improving the corrosion resistance of an aqueous organic protective coating, in order to solve the problem that boron nitride is easy to generate coagulation in a solvent, the modified boron nitride nanosheet is prepared by modifying boron nitride through 3-Aminopropyltriethoxysilane (APTES), and the modified boron nitride nanosheet solves the problem that boron nitride is difficult to disperse in water, can be well dispersed in an aqueous epoxy coating, is used for preparing the aqueous organic protective coating, and can greatly enhance the corrosion resistance of the aqueous epoxy resin coating.
Description
Technical Field
The invention belongs to the technical field of metal corrosion protection, and particularly relates to a preparation method of a modified boron nitride nanosheet and application of the modified boron nitride nanosheet in improving corrosion resistance of an aqueous organic protective coating.
Background
Most metals and alloys thereof can be corroded frequently, which causes great economic loss to national economy of China. At present, there are many means for protecting metal corrosion, such as organic coating protection, corrosion inhibitor protection, electrochemical protection, etc. Among them, the organic coating protection method is most commonly used, and particularly, the epoxy resin organic coating protection method is favored because of excellent corrosion resistance, electrical insulation, and strong adhesion to a metal substrate. Currently, the epoxy coatings used to prepare organic epoxy coatings are mainly solvent-based epoxy coatings and water-based epoxy coatings. The solvent type epoxy resin coating has a compact structure and excellent barrier property, but volatile substances (xylene, isopropanol, ethanol and the like) are added into the coating in a certain proportion to improve the performance of the solvent type epoxy resin coating, so that the solvent type epoxy resin coating has great harm to the environment and human health. Meanwhile, in the curing process of the solvent type epoxy resin coating, micropores or microcracks are easily formed due to solvent volatilization, so that the long-term anticorrosion effect of the solvent type epoxy resin coating on a metal matrix is greatly limited. The water-based epoxy resin coating has the advantages of no toxicity, no combustion, no environmental pollution, energy conservation and the like, so the environment-friendly water-based epoxy resin coating is more and more attracted by people. However, waterborne epoxy coatings are inferior to solvent-borne epoxy coatings in many properties (e.g., chemical resistance, abrasion resistance, hardness, water resistance, etc.).
In the past decade, graphene, a two-dimensional nanomaterial, has attracted considerable attention in the field of epoxy coatings due to its strong permeation resistance, chemical inertness, hydrophobicity, thermal stability, and excellent mechanical properties. However, the fatal problem of graphene is its high conductivity, which makes it likely to cause galvanic corrosion with a metal substrate even in a corrosive medium (H) for a long period of time2O、O2Cl-) accelerate the dissolution of the metal. It is therefore particularly important to suppress galvanic corrosion by passivating graphene or exploring alternative materials for low conductivity insulation. Hexagonal boron nitride (h-BN), also known as white graphene, is an ultra-wideband gap insulating material, and has attracted extensive attention in the fields of metal corrosion protection and the like because of its excellent barrier property and the ability to fundamentally avoid galvanic corrosion. However, it is possible to use a single-layer,different from graphene oxide, the surface of hexagonal boron nitride has no functional group, so that coagulation is easy to occur when the hexagonal boron nitride is dispersed in a solvent, and therefore, some hydrophilic functional groups must be grafted on the surface of the hexagonal boron nitride by a covalent bond or non-covalent bond method, so that the dispersion stability of the hexagonal boron nitride in the water-based epoxy resin can be greatly improved, and the corrosion resistance of the water-based paint is further enhanced.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides a preparation method of a modified boron nitride nanosheet, the modified boron nitride nanosheet prepared by the method solves the problem that boron nitride is difficult to disperse in water, can be well dispersed in a water-based epoxy coating, is used for preparing a water-based organic protective coating, and can greatly enhance the corrosion resistance of the water-based epoxy resin coating.
In order to achieve the purpose, the invention adopts the technical scheme that:
the invention provides a preparation method of a modified boron nitride nanosheet, which comprises the following steps:
s1, dispersing boron nitride (h-BN) powder in an organic solvent, then adding sodium hydroxide and lithium chloride, and obtaining a dispersion liquid after hydrothermal treatment;
s2, centrifuging the dispersion liquid obtained in the step S1, and taking supernatant to obtain hydroxylated boron nitride nanosheet dispersion liquid;
s3, filtering, washing and drying the nanosheet dispersion liquid obtained in the step S2 to obtain hydroxylated boron nitride nanosheet powder;
s4, adding 3-Aminopropyltriethoxysilane (APTES) into an ethanol solution, heating and stirring to fully hydrolyze the 3-aminopropyltriethoxysilane, adding the hydroxylated boron nitride nanosheet powder obtained in the step S3, stirring, filtering, washing and drying to obtain the modified boron nitride nanosheet (APTES @ h-BN nanosheet for short).
Preferably, the concentration of the boron nitride in the organic solvent is 4-7 mg/mL. Further, the concentration of the boron nitride in the organic solvent was 5 mg/mL.
Preferably, the mass ratio of the sodium hydroxide to the boron nitride is 4-6:1, and the mass ratio of the lithium chloride to the boron nitride is 1: 40-70. Further, the mass ratio of the sodium hydroxide to the boron nitride is 5:1, and the mass ratio of the lithium chloride to the boron nitride is 1: 50.
Preferably, the hydrothermal treatment is hydrothermal treatment at 140-160 ℃ for 5-7 h. Further, the hydrothermal treatment is hydrothermal treatment at 150 ℃ for 6 h.
Preferably, the concentration of the 3-aminopropyltriethoxysilane in the ethanol solution is 1-1.5 mg/mL. Further, the concentration of the 3-aminopropyltriethoxysilane in the ethanol solution was 1.5 mg/mL.
Preferably, the mass ratio of the hydroxylated boron nitride nanosheet powder to the 3-aminopropyltriethoxysilane is 10: 3.
Preferably, the organic solvent includes, but is not limited to, isopropanol.
Preferably, the centrifugation is carried out at 1300-.
Preferably, the heating stirring is continuous stirring in an oil bath at the temperature of 55-65 ℃ for 20-40 min.
Preferably, the stirring of step S4 is at 70 ℃ to 90 ℃ for 5 to 7 hours.
The invention also provides a modified boron nitride nanosheet (APTES @ h-BN nanosheet) prepared by the preparation method.
The invention also provides application of the modified boron nitride nanosheet (APTES @ h-BN nanosheet) in improving the corrosion resistance of the aqueous organic protective coating.
The h-BN powder is difficult to uniformly disperse in water before being modified, and serious agglomeration phenomenon can occur after the h-BN powder is stood for a short time, so that a large number of defect structures can be generated due to agglomeration of agglomerated boron nitride when the h-BN powder is added into the water-based epoxy resin coating, a corrosive medium can easily and quickly contact with a metal substrate through the defect structures, and the coating loses the metal corrosion protection effect.
The APTES can react with hydroxyl on the surface of h-BN, so that covalent bond modification of boron nitride is realized (see figure 1). Meanwhile, the APTES contains hydrophilic-NH2Therefore, the modified boron nitride nanosheets can be well dispersed in the aqueous epoxy coating, and the path of a corrosive medium entering the surface of the metal substrate can be further prolonged (see fig. 2). And Si-O in the APTES can generate a crosslinking reaction with an epoxy group in the epoxy resin, so that the compactness of the coating can be further improved. Therefore, the corrosion resistance of the waterborne epoxy resin coating can be greatly enhanced through APTES @ h-BN nanosheet modification.
The invention also provides a preparation method of the corrosion-resistant water-based organic protective coating, which is characterized in that the modified boron nitride nanosheet is added into water, and after ultrasonic treatment, water-based epoxy resin (WEP) is added to obtain water-based epoxy emulsion; and adding a curing agent into the emulsion after the emulsion is subjected to rotary evaporation, and finally stirring and defoaming to obtain the corrosion-resistant water-based organic protective coating, also called APTES-hBN/water-based epoxy organic coating, which is called APTES @ h-BN/WEP for short.
Preferably, the mass ratio of the modified boron nitride nanosheet to the aqueous epoxy resin is 0.25 wt% -1 wt%. Further, the mass ratio of the modified boron nitride nanosheet to the aqueous epoxy resin is 0.50 wt% -0.75 wt%. Specifically, the mass ratio of the modified boron nitride nanosheet to the aqueous epoxy resin is 0.50 wt%.
Preferably, the mass ratio of the water to the water-based epoxy resin is 1: 1.
preferably, the weight ratio of the waterborne epoxy resin to the curing agent is 2: 1.
preferably, the water-based epoxy coating is coated on the surface of the treated Q235 carbon steel, and is cured for 2 hours at room temperature and then cured for 6 hours at 60 ℃ to obtain the corrosion-resistant water-based organic protective coating.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a preparation method of a modified boron nitride nanosheet, wherein the modified boron nitride nanosheet is prepared by modifying boron nitride through 3-Aminopropyltriethoxysilane (APTES), and the modified boron nitride nanosheet solves the problem that the boron nitride is difficult to disperse in water, can be well dispersed in a water-based epoxy coating, is used for preparing a water-based organic protective coating, and can greatly enhance the corrosion resistance of the water-based epoxy resin coating.
Drawings
FIG. 1 is an infrared image of boron nitride and modified boron nitride nanosheets of the present invention;
FIG. 2 is a graph illustrating the corrosion resistance mechanism of the aqueous organic protective coating of the present invention;
FIG. 3 is an electrochemical test chart of an aqueous organic protective coating according to the present invention;
fig. 4 is a static contact angle test chart of the aqueous organic protective coating in the invention.
Detailed Description
The following further describes the embodiments of the present invention. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The experimental procedures in the following examples were carried out by conventional methods unless otherwise specified, and the test materials used in the following examples were commercially available by conventional methods unless otherwise specified.
Example 1 preparation of modified boron nitride (APTES @ h-BN) nanoplates
(1) Weighing 1g h-BN powder, dispersing in 200mL isopropanol (concentration is 5mg/mL), adding 5g sodium hydroxide and 20mg lithium chloride, and performing hydrothermal treatment at 150 ℃ for 6h to obtain a dispersion liquid;
(2) centrifuging the dispersion liquid at the rotating speed of 1500rpm/min for 10min, and taking supernatant liquid to obtain hydroxylated boron nitride nanosheet dispersion liquid;
(3) repeatedly washing the nanosheet dispersion liquid for three times by using deionized water after filtration, and then drying the nanosheet dispersion liquid in a vacuum drying oven at 60 ℃ for 12 hours to obtain hydroxylated boron nitride nanosheet powder;
(4) weighing 150mg of 3-Aminopropyltriethoxysilane (APTES) in 100mL of absolute ethanol solution, heating the obtained mixed solution to 60 ℃ in an oil bath, and continuously stirring for 30min, thereby promoting the complete hydrolysis of the APTES; and then dispersing 0.5g of hydroxylated boron nitride nanosheet powder in the mixed solution, stirring for 6h at 80 ℃, filtering to obtain a dispersion, repeatedly washing with deionized water for three times, and finally drying for 8h at 80 ℃ to obtain APTES @ h-BN nanosheet powder.
Example 2 preparation of modified boron nitride (APTES @ h-BN) nanoplates
(1) Weighing 1g h-BN powder, dispersing in 150mL of isopropanol (the concentration is 6.67mg/mL), adding 4g of sodium hydroxide and 15mg of lithium chloride, and performing hydrothermal treatment for 7h at 140 ℃ to obtain a dispersion liquid;
(2) centrifuging the dispersion liquid at the rotating speed of 1300rpm/min for 15min, and taking supernatant liquid to obtain hydroxylated boron nitride nanosheet dispersion liquid;
(3) repeatedly washing the nanosheet dispersion liquid for three times by using deionized water after filtration, and then drying the nanosheet dispersion liquid in a vacuum drying oven at 60 ℃ for 12 hours to obtain hydroxylated boron nitride nanosheet powder;
(4) weighing 150mg of 3-Aminopropyltriethoxysilane (APTES) in 125mL of absolute ethanol solution, heating the obtained mixed solution to 55 ℃ in an oil bath, and continuously stirring for 40min, thereby promoting the complete hydrolysis of the APTES; and then dispersing 0.5g of hydroxylated boron nitride nanosheet powder in the mixed solution, stirring for 7h at 70 ℃, filtering to obtain a dispersion, repeatedly washing with deionized water for three times, and finally drying for 8h at 80 ℃ to obtain APTES @ h-BN nanosheet powder.
Example 3 preparation of modified boron nitride (APTES @ h-BN) nanoplates
(1) Weighing 1g h-BN powder, dispersing in 250mL of isopropanol (the concentration is 4mg/mL), then adding 6g of sodium hydroxide and 25mg of lithium chloride, and carrying out hydrothermal treatment for 5h at 160 ℃ to obtain a dispersion liquid;
(2) centrifuging the dispersion liquid at the rotating speed of 1700rpm/min for 7min, and taking supernatant liquid to obtain hydroxylated boron nitride nanosheet dispersion liquid;
(3) repeatedly washing the nanosheet dispersion liquid for three times by using deionized water after filtration, and then drying the nanosheet dispersion liquid in a vacuum drying oven at 60 ℃ for 12 hours to obtain hydroxylated boron nitride nanosheet powder;
(4) weighing 150mg of 3-Aminopropyltriethoxysilane (APTES) in 150mL of absolute ethanol solution, heating the obtained mixed solution to 65 ℃ in an oil bath, and continuously stirring for 20min, thereby promoting the complete hydrolysis of the APTES; and then dispersing 0.5g of hydroxylated boron nitride nanosheet powder in the mixed solution, stirring for 5h at 90 ℃, filtering to obtain a dispersion, repeatedly washing with deionized water for three times, and finally drying for 8h at 80 ℃ to obtain APTES @ h-BN nanosheet powder.
EXAMPLE 4 preparation of Corrosion resistant waterborne organic protective coatings/coatings (APTES @ h-BN/WEP)
(1) Weighing 25mg of APTES @ h-BN nanosheet powder in example 1, performing ultrasonic treatment in 10g of deionized water for 15min, adding 10g of waterborne epoxy resin (WE51) and stirring at room temperature for 15min, and performing rotary evaporation on the obtained waterborne epoxy emulsion to remove excessive moisture, so that a large number of pores or cracks can be greatly avoided in the curing process of excessive moisture;
(2) pouring out the emulsion after rotary evaporation, then adding 5g of WH115 curing agent (waterborne epoxy resin: curing agent: 2: 1, mass ratio), fully stirring for 5min, placing in a defoaming machine for high-speed vacuum centrifugal defoaming, and preparing to obtain a waterborne epoxy coating;
(3) coating the water-based epoxy coating on the surface of the treated Q235 carbon steel, curing for 2h at room temperature, then transferring into an oven, and curing for 6h at 60 ℃ to prepare the corrosion-resistant water-based organic protective coating (also called APTES-hBN/water-based epoxy organic coating), which is named APTES @ h-BN0.25wt％/WEP。
EXAMPLE 5 preparation of Corrosion resistant waterborne organic protective coatings/coatings (APTES @ h-BN/WEP)
(1) Weighing 50mg of APTES @ h-BN nanosheet powder in example 1, performing ultrasonic treatment in 10g of deionized water for 15min, adding 10g of waterborne epoxy resin (WE51) and stirring at room temperature for 15min, and performing rotary evaporation on the obtained waterborne epoxy emulsion to remove excessive moisture, so that a large number of pores or cracks can be greatly avoided in the curing process of excessive moisture;
the corrosion-resistant aqueous organic waterproof prepared by the steps (2) and (3) in the same way as the example 2The protective coating (also known as APTES-hBN/waterborne epoxy organic coating) is named APTES @ h-BN0.50wt％/WEP。
EXAMPLE 6 preparation of Corrosion resistant waterborne organic protective coatings/coatings (APTES @ h-BN/WEP)
(1) Weighing 75mg of APTES @ h-BN nanosheet powder in example 1, performing ultrasonic treatment in 10g of deionized water for 15min, adding 10g of waterborne epoxy resin (WE51) and stirring at room temperature for 15min, and performing rotary evaporation on the obtained waterborne epoxy emulsion to remove excessive moisture, so that a large number of pores or cracks can be greatly avoided in the curing process of excessive moisture;
the steps (2) and (3) are the same as the step 2, and the corrosion-resistant waterborne organic protective coating (also called APTES-hBN/waterborne epoxy organic coating) is prepared and named APTES @ h-BN0.75wt％/WEP。
EXAMPLE 7 preparation of Corrosion resistant waterborne organic protective coating/coating (APTES @ h-BN/WEP)
(1) Weighing 100mg of APTES @ h-BN nanosheet powder in example 1, performing ultrasonic treatment in 10g of deionized water for 15min, adding 10g of waterborne epoxy resin (WE51) and stirring at room temperature for 15min, and performing rotary evaporation on the obtained waterborne epoxy emulsion to remove excessive moisture, so that a large number of pores or cracks can be greatly avoided in the curing process of excessive moisture;
the steps (2) and (3) are the same as the step 2, and the corrosion-resistant waterborne organic protective coating (also called APTES-hBN/waterborne epoxy organic coating) is prepared and named APTES @ h-BN1wt％/WEP。
Comparative example 1 preparation of Corrosion resistant waterborne organic protective coating/coating (APTES @ h-BN/WEP)
(1) Adding 10g of deionized water into 10g of waterborne epoxy resin (WE51), stirring for 15min at room temperature, and removing excessive moisture from the obtained waterborne epoxy emulsion by rotary evaporation, so that a large amount of pores or cracks formed in the curing process of excessive moisture can be greatly avoided;
the steps (2) and (3) are the same as the step 2, and the corrosion-resistant waterborne organic protective coating (also called APTES-hBN/waterborne epoxy organic coating) is prepared and named APTES @ h-BN0wt％/WEP。
Experimental example 1 electrochemical Performance test
The Q235 steel sheets coated with the aqueous organic protective coating prepared in examples 4 to 7 and comparative example 1 were soaked in 3.5 wt% NaCl solution for 50d, and then subjected to electrochemical impedance spectroscopy and Tafel curve tests. The test adopts a classical three-electrode system, wherein a saturated AgCl electrode is used as a reference electrode, a platinum sheet is used as an auxiliary electrode, and a Q235 steel sheet coated with a water-based organic protective coating is used as a working electrode, before the test, the Q235 steel sheet is soaked in 3.5 wt% NaCl solution for 30 minutes to enable the open circuit potential to reach a stable state, during the test, the disturbance amplitude of impedance measured by the three-electrode system is 10mV, and the test frequency is 10mV5-10-2Hz。
As can be seen from Table 1, after being soaked in 3.5 wt% NaCl solution for 50 days, the impedance values of the waterborne organic protective coatings prepared by the method of the invention are all improved to a certain extent, wherein, when the addition amount of APTES @ h-BN is 0.5 wt%, the impedance value of the waterborne organic protective coating is the highest, and the | Z | of the coating is smooth0.01Hz＝6.04×107(Ω/cm2) 0.75 wt% APTES @ h-BN added next to the amount added. Therefore, the APTES @ h-BN/WEP coating can enhance the corrosion resistance of the waterborne epoxy coating.
TABLE 1 impedance value (Ω/cm) of Q235 steel sheet coated with aqueous organic protective coating after soaking for 50d2)
| Group of | Name of coating | Impedance value |
| Example 4 | APTES@h-BN0.25wt％/WEP | 1.44×107 |
| Example 5 | APTES@h-BN0.50wt％/WEP | 6.04×107 |
| Example 6 | APTES@h-BN0.75wt％/WEP | 3.31×107 |
| Example 7 | APTES@h-BN1wt％/WEP | 1.49×107 |
| Comparative example 1 | APTES@h-BN0wt％/WEP | 1.39×107 |
The two graphs in fig. 3 are bode graphs obtained by electrochemical impedance spectroscopy, the impedance value corresponding to the low frequency can well reflect the electrochemical reaction between the coating and the metal, and the higher the impedance value of the low frequency is, the better the corrosion resistance of the coating is. As can be seen from the left panel of FIG. 3, APTES @ h-BN0.50wt％WEP at 10-2The impedance values at Hz are higher than those of the other samples, and the right graph of FIG. 3 is a graph of the phase angle as a function of time and frequency, and it can be seen from the graph that the impedance values at the low frequency stage (100-10)-2Hz)，APTES@h-BN0.50wt％The phase angle of the/WEP sample is higher than that of the other samples, thus indicating APTES @ h-BN0.50wt％The best corrosion resistance of/WEP.
Experimental example 2 static Water contact Angle test
To test the permeation resistance of the aqueous organic protective coating of the present invention to corrosive solutions, static water contact angle measurements were performed on the Q235 steel sheets coated with the aqueous organic protective coating prepared in examples 4-7 and comparative example 1.
Experiments show that the micro-nano structure of the surface of the coating can be changed by adding APTES @ h-BN with different contents into a waterborne epoxy resin system, so that the permeation resistance of the coating is influenced. It was also found that the water contact angle of the coating was the highest at 112.1 deg. when the APTES @ h-BN content was 0.5 wt% (FIG. 4). Therefore, the corrosion resistance of the water-based organic protective coating is strongest when the addition amount of APTES @ h-BN is 0.5 wt% as proved by a contact angle test.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. It will be apparent to those skilled in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, and the scope of protection is still within the scope of the invention.
Claims (10)
1. A preparation method of a modified boron nitride nanosheet is characterized by comprising the following steps:
s1, dispersing boron nitride powder in an organic solvent, adding sodium hydroxide and lithium chloride, and carrying out hydrothermal treatment to obtain a dispersion liquid;
s2, centrifuging the dispersion liquid obtained in the step S1, and taking supernatant to obtain hydroxylated boron nitride nanosheet dispersion liquid;
s3, filtering, washing and drying the nanosheet dispersion liquid obtained in the step S2 to obtain hydroxylated boron nitride nanosheet powder;
s4, adding 3-aminopropyltriethoxysilane into the ethanol solution, heating and stirring to fully hydrolyze the 3-aminopropyltriethoxysilane, adding the hydroxylated boron nitride nanosheet powder obtained in the step S3, stirring, filtering, washing and drying to obtain the modified boron nitride nanosheet.
2. A method for preparing modified boron nitride nanosheets according to claim 1, wherein the concentration of boron nitride in the organic solvent is from 4 to 7 mg/mL.
3. The preparation method of a modified boron nitride nanosheet according to claim 1, wherein the mass ratio of sodium hydroxide to boron nitride is 4-6:1, and the mass ratio of lithium chloride to boron nitride is 1: 40-70.
4. The preparation method of a modified boron nitride nanosheet according to claim 1, wherein the hydrothermal treatment is a hydrothermal treatment at 140 ℃ -160 ℃ for 5-7 h.
5. The preparation method of modified boron nitride nanosheets of claim 1, wherein the concentration of the 3-aminopropyltriethoxysilane in the ethanol solution is 1-1.5 mg/mL.
6. The method for preparing modified boron nitride nanosheets according to claim 1, wherein the mass ratio of hydroxylated boron nitride nanosheet powder to 3-aminopropyltriethoxysilane is 10: 3.
7. Modified boron nitride nanosheets prepared by the preparation method of any one of claims 1-6.
8. Use of the modified boron nitride nanoplates of claim 7 to improve the corrosion resistance of aqueous organic protective coatings.
9. A preparation method of a corrosion-resistant aqueous organic protective coating is characterized in that the modified boron nitride nanosheet of claim 7 is added into water, subjected to ultrasonic treatment and then added into aqueous epoxy resin to obtain an aqueous epoxy emulsion; and (3) adding a curing agent into the emulsion after rotary evaporation, and finally stirring and defoaming to obtain the corrosion-resistant aqueous organic protective coating.
10. The preparation method of the corrosion-resistant aqueous organic protective coating according to claim 9, wherein the mass ratio of the modified boron nitride nanosheet to the aqueous epoxy resin is 0.25 wt% to 1 wt%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110254885.8A CN113004736A (en) | 2021-03-09 | 2021-03-09 | Preparation method of modified boron nitride nanosheet and application of modified boron nitride nanosheet in improving corrosion resistance of aqueous organic protective coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110254885.8A CN113004736A (en) | 2021-03-09 | 2021-03-09 | Preparation method of modified boron nitride nanosheet and application of modified boron nitride nanosheet in improving corrosion resistance of aqueous organic protective coating |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN113004736A true CN113004736A (en) | 2021-06-22 |
Family
ID=76402742
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110254885.8A Pending CN113004736A (en) | 2021-03-09 | 2021-03-09 | Preparation method of modified boron nitride nanosheet and application of modified boron nitride nanosheet in improving corrosion resistance of aqueous organic protective coating |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113004736A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113621300A (en) * | 2021-08-10 | 2021-11-09 | 中山大学 | Nanosheet composite coating and preparation method and application thereof |
| CN113637338A (en) * | 2021-08-18 | 2021-11-12 | 天津大学 | Modified hexagonal boron nitride, water-based anti-oxidation anticorrosive coating and preparation method thereof |
| CN113698848A (en) * | 2021-08-10 | 2021-11-26 | 中山大学 | Water-based nanosheet composite coating and preparation method and application thereof |
| CN114316750A (en) * | 2022-01-05 | 2022-04-12 | 方亨 | Method for improving corrosion resistance of vinyl resin |
| CN114804042A (en) * | 2022-06-15 | 2022-07-29 | 罗周艾 | Hexagonal boron nitride nanosheet and preparation method thereof |
| CN114874453A (en) * | 2022-06-24 | 2022-08-09 | 中国人民解放军国防科技大学 | BN nanosheet modified polycarbosilane and synthesis method thereof |
| CN115322646A (en) * | 2022-09-27 | 2022-11-11 | 合肥工业大学 | Sintered NdFeB magnet surface corrosion-resistant coating and preparation method thereof |
| CN115595041A (en) * | 2022-10-25 | 2023-01-13 | 中国科学院兰州化学物理研究所（Cn） | Epoxy coating with directionally arranged boron nitride nanosheets induced by electromagnetic field |
| CN116285588A (en) * | 2023-04-17 | 2023-06-23 | 海信冰箱有限公司 | Paint, preparation method and application thereof, and refrigerator |
| CN116426172A (en) * | 2023-04-12 | 2023-07-14 | 广东吉美帮新材料有限公司 | Corrosion-resistant acid-alkali-resistant water-based rubber coating and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857195A (en) * | 2010-05-21 | 2010-10-13 | 哈尔滨工业大学 | Efficient mechanical method for peeling layered compounds |
| CN103058180A (en) * | 2013-01-23 | 2013-04-24 | 中国科学院苏州纳米技术与纳米仿生研究所 | Novel synthetic method for graphene |
| US20150184055A1 (en) * | 2012-09-19 | 2015-07-02 | Momentive Performance Materials Inc. | Thermally conductive plastic compositions, extrusion apparatus and methods for making thermally conductive plastics |
| CN109021233A (en) * | 2018-06-26 | 2018-12-18 | 同济大学 | The high thermal stability composite polyimide material and preparation method thereof of the material of boron nitride nanometer containing amino functional |
| CN109250693A (en) * | 2018-10-10 | 2019-01-22 | 深圳烯材科技有限公司 | A kind of method that mechanical force intercalation stripping prepares inorganic two-dimension nano materials |
| CN109535658A (en) * | 2018-12-04 | 2019-03-29 | 河北工业大学 | A kind of hexagonal boron nitride/epoxy resin composite material preparation method of high heat conductance |
| CN110343291A (en) * | 2019-07-31 | 2019-10-18 | 武汉工程大学 | The preparation method and Water-borne inflation type refractory coating of modified hexagonal boron nitride fire retardant |
| CN111039274A (en) * | 2018-10-12 | 2020-04-21 | 中国科学院化学研究所 | Liquid phase stripping method of graphdiyne |
| US20200262703A1 (en) * | 2017-10-27 | 2020-08-20 | National Research Council Of Canada | Modified boron nitride nanotubes and solutions thereof |
-
2021
- 2021-03-09 CN CN202110254885.8A patent/CN113004736A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857195A (en) * | 2010-05-21 | 2010-10-13 | 哈尔滨工业大学 | Efficient mechanical method for peeling layered compounds |
| US20150184055A1 (en) * | 2012-09-19 | 2015-07-02 | Momentive Performance Materials Inc. | Thermally conductive plastic compositions, extrusion apparatus and methods for making thermally conductive plastics |
| CN103058180A (en) * | 2013-01-23 | 2013-04-24 | 中国科学院苏州纳米技术与纳米仿生研究所 | Novel synthetic method for graphene |
| US20200262703A1 (en) * | 2017-10-27 | 2020-08-20 | National Research Council Of Canada | Modified boron nitride nanotubes and solutions thereof |
| CN109021233A (en) * | 2018-06-26 | 2018-12-18 | 同济大学 | The high thermal stability composite polyimide material and preparation method thereof of the material of boron nitride nanometer containing amino functional |
| CN109250693A (en) * | 2018-10-10 | 2019-01-22 | 深圳烯材科技有限公司 | A kind of method that mechanical force intercalation stripping prepares inorganic two-dimension nano materials |
| CN111039274A (en) * | 2018-10-12 | 2020-04-21 | 中国科学院化学研究所 | Liquid phase stripping method of graphdiyne |
| CN109535658A (en) * | 2018-12-04 | 2019-03-29 | 河北工业大学 | A kind of hexagonal boron nitride/epoxy resin composite material preparation method of high heat conductance |
| CN110343291A (en) * | 2019-07-31 | 2019-10-18 | 武汉工程大学 | The preparation method and Water-borne inflation type refractory coating of modified hexagonal boron nitride fire retardant |
Non-Patent Citations (4)
| Title |
|---|
| WANG, NING等: ""A universal method for large-yield and high-concentration exfoliation of two-dimensional hexagonal boron nitride nanosheets"", 《MATERIALS TODAY》 * |
| WU, YANGMIN等: ""Investigating the anti-corrosion behaviors of the waterborne epoxy composite coatings with barrier and inhibition roles on mild steel"", 《PROGRESS IN ORGANIC COATINGS》 * |
| YU, JINGJING等: ""Anti-corrosion mechanism of 2D nanosheet materials in waterborne epoxy coatings"", 《SURFACE TOPOGRAPHY-METROLOGY AND PROPERTIES》 * |
| 孙九龙等: ""氮化硼纳米片在重防腐涂层中的应用进展"", 《化学学报》 * |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113621300B (en) * | 2021-08-10 | 2023-02-17 | 中山大学 | Nanosheet composite coating and preparation method and application thereof |
| CN113698848A (en) * | 2021-08-10 | 2021-11-26 | 中山大学 | Water-based nanosheet composite coating and preparation method and application thereof |
| CN113621300A (en) * | 2021-08-10 | 2021-11-09 | 中山大学 | Nanosheet composite coating and preparation method and application thereof |
| CN113637338A (en) * | 2021-08-18 | 2021-11-12 | 天津大学 | Modified hexagonal boron nitride, water-based anti-oxidation anticorrosive coating and preparation method thereof |
| CN114316750A (en) * | 2022-01-05 | 2022-04-12 | 方亨 | Method for improving corrosion resistance of vinyl resin |
| CN114316750B (en) * | 2022-01-05 | 2022-06-07 | 方亨 | Method for improving corrosion resistance of vinyl resin |
| CN114804042A (en) * | 2022-06-15 | 2022-07-29 | 罗周艾 | Hexagonal boron nitride nanosheet and preparation method thereof |
| CN114874453A (en) * | 2022-06-24 | 2022-08-09 | 中国人民解放军国防科技大学 | BN nanosheet modified polycarbosilane and synthesis method thereof |
| CN114874453B (en) * | 2022-06-24 | 2023-03-31 | 中国人民解放军国防科技大学 | BN nanosheet modified polycarbosilane and synthesis method thereof |
| CN115322646A (en) * | 2022-09-27 | 2022-11-11 | 合肥工业大学 | Sintered NdFeB magnet surface corrosion-resistant coating and preparation method thereof |
| CN115595041A (en) * | 2022-10-25 | 2023-01-13 | 中国科学院兰州化学物理研究所（Cn） | Epoxy coating with directionally arranged boron nitride nanosheets induced by electromagnetic field |
| CN116426172A (en) * | 2023-04-12 | 2023-07-14 | 广东吉美帮新材料有限公司 | Corrosion-resistant acid-alkali-resistant water-based rubber coating and preparation method thereof |
| CN116426172B (en) * | 2023-04-12 | 2024-01-12 | 广东吉美帮新材料有限公司 | Corrosion-resistant acid-alkali-resistant water-based rubber coating and preparation method thereof |
| CN116285588A (en) * | 2023-04-17 | 2023-06-23 | 海信冰箱有限公司 | Paint, preparation method and application thereof, and refrigerator |
| CN116285588B (en) * | 2023-04-17 | 2024-02-02 | 海信冰箱有限公司 | Paint, preparation method and application thereof, and refrigerator |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113004736A (en) | Preparation method of modified boron nitride nanosheet and application of modified boron nitride nanosheet in improving corrosion resistance of aqueous organic protective coating | |
| Zhang et al. | Poly (dopamine) assisted epoxy functionalization of hexagonal boron nitride for enhancement of epoxy resin anticorrosion performance | |
| Cui et al. | Polydimethylsiloxane-titania nanocomposite coating: fabrication and corrosion resistance | |
| CN110054965B (en) | Modified graphene oxide co-cured waterborne epoxy resin coating and preparation method thereof | |
| CN110157296B (en) | Graphite-like phase carbon nitride/epoxy resin corrosion-resistant coating and preparation method and application thereof | |
| Liu et al. | Corrosion protection of silane coatings modified by carbon nanotubes on stainless steel | |
| JP2020533424A (en) | Graphene nano-container-based paints, self-healing coating layers and their manufacturing methods and applications | |
| CN108659671B (en) | Lignin/graphene-based composite anticorrosive coating and preparation method and application thereof | |
| CN114276743B (en) | MXene and carbon nanotube synergistically modified polyurethane anticorrosive paint and preparation method and construction process thereof | |
| Tavandashti et al. | Corrosion protection evaluation of silica/epoxy hybrid nanocomposite coatings to AA2024 | |
| Okechi Arukalam et al. | Hydroxypropyl methylcellulose as a polymeric corrosion inhibitor for aluminium | |
| Li et al. | Enhancing the Corrosion Resistance of Epoxy Coatings by Impregnation with a Reduced Graphene Oxide‐Hydrophobic Ionic Liquid Composite | |
| El-Mahdy et al. | Application of Silica/polyacrylamide nanocomposite as Anticorrosive layer for Steel | |
| Ansari et al. | Study on the protective function of cloisite incorporated silane sol–gel coatings cured at different conditions | |
| Yan et al. | Preparation and properties of epoxy/basalt flakes anticorrosive coatings | |
| CN108531045A (en) | A kind of aqueous epoxide resin paint and its preparation method and application that graphene is modified | |
| CN113621300B (en) | Nanosheet composite coating and preparation method and application thereof | |
| Zhu et al. | Investigation of the anticorrosion layer of reinforced steel based on graphene oxide in simulated concrete pore solution with 3 wt.% NaCl | |
| Ban et al. | Triethanolamine modified graphene oxide for epoxy resin‐based coatings: Corrosion inhibition on metal substrates | |
| He et al. | Synthesis and properties of iron oxide coated carbon nanotubes hybrid materials and their use in epoxy coatings | |
| Yin et al. | Synthesis of phytic acid-modified chitosan and the research of the corrosion inhibition and antibacterial properties | |
| Wang et al. | Corrosion protection of epoxy coatings containing ZSM‐5 zeolites on Mg–Li alloys | |
| Ge et al. | Si3N4@ RGO hybrids for epoxy coatings with enhanced anticorrosion performance | |
| Wonnie Ma et al. | A comparative study of corrosion resistance of epoxy-based coating incorporated chitosan, silica and hybrid compound of chitosan/silica on mild steel | |
| Wang et al. | Effect of hybrid aluminum dihydrogen phosphate on the corrosion resistance of PTFE composite ceramic coatings |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210622 |
|
| RJ01 | Rejection of invention patent application after publication |