CN115746649A - Anticorrosive paint for metal and preparation and application thereof - Google Patents
Anticorrosive paint for metal and preparation and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of anticorrosive coatings, and particularly relates to an anticorrosive coating for metal, and preparation and application thereof. The anticorrosive coating for metals comprises the following raw materials in percentage by mass: 80-95% of a photocureable coating precursor and 5-20% of nano particles; the raw materials of the photo-curing coating precursor comprise a hydrophobic agent, a cross-linking agent and a photoinitiator; the hydrophobic agent is unsaturated oleate with polyfunctional double bonds; the cross-linking agent is a mercapto derivative. The anticorrosive coating avoids the use of organic solvents, is simple and environment-friendly, has short flow, is suitable for industrial processing production, and has high utilization rate and excellent anticorrosive performance; besides the anticorrosion performance of the base material, the functional nano particles in the coating can endow the coating with light aging resistance and high temperature resistance, so that the application of the anticorrosion coating in a complex environment is met.
Description
Technical Field
The invention belongs to the technical field of anticorrosive coatings, and particularly relates to an anticorrosive coating for metal, and preparation and application thereof.
Background
The metal material is damaged by the surrounding medium, which is called metal Corrosion (Metallic Corrosion). Corrosion of metals is the most common form of corrosion. During corrosion, a chemical or electrochemical multiphase reaction occurs at the interface of the metal, causing the metal to transition to an oxidized (ionic) state. This can significantly reduce the mechanical properties of the metal material such as strength, plasticity, toughness, etc., destroy the geometric shape of the metal member, increase the wear between parts, deteriorate the physical properties of electricity, optics, etc., shorten the service life of the equipment, and even cause disastrous accidents such as fire, explosion, etc. Thus, metal corrosion has raised concerns about safety.
The metal corrosion is prevented by adopting a proper method aiming at the metal corrosion reason, and the common methods comprise the following steps: (1) Changing the internal structure of metal, for example, making various corrosion-resistant alloys, such as stainless steel made by adding chromium, nickel and the like into common steel; (2) The protective layer method is to cover the surface of metal with a protective layer to isolate the metal product from the surrounding corrosive medium, thereby preventing corrosion. The protective layer method mainly comprises three modes: a. coating engine oil, vaseline and paint on the surface of the steel part or covering enamel, plastic and other corrosion-resistant non-metallic materials on the surface of the steel part; b. plating a layer of metal which is not easy to corrode, such as zinc, tin, chromium, nickel and the like on the surface of the steel by using methods such as electroplating, hot-dip plating, spraying and the like, wherein the metal is often oxidized to form a compact oxide film so as to prevent water, air and the like from corroding the steel; c. a layer of fine and stable oxide film is generated on the surface of steel by a chemical method. For example, a layer of fine black ferroferric oxide film is formed on the surface of iron and steel products such as machine parts, guns and the like.
Among them, organic coatings are considered the most versatile strategy for preventing corrosion of metals due to their good aging and processing properties, and are widely used in mechanical and marine corrosion protection applications. However, purely organic coatings do not provide a good combination of properties such as physical barrier, corrosion resistance, and chemical inertness. The hydrophobic coating is generally composed of a low surface energy substance and a micro-nano scale rough structure, and can shield a corrosive medium from contacting a metal substrate due to excellent barrier property, so that the metal substrate is endowed with long-term corrosion resistance. In addition, the coating preparation involves a long-flow process, severe environmental pollution, high cost, low coating utilization rate and the like, which does not meet the requirements of industrial mass production, application and environmental protection.
The invention patent with the application number of 201910162015.0 discloses an anticorrosive carbon nanotube/silane composite super-hydrophobic coating and a preparation method thereof. The method mainly comprises the following steps of immersing a degreased and hydroxylated galvanized steel substrate into a silane solution containing a carbon nano tube carrying a corrosion inhibitor, inorganic nano particles and a low-surface-energy modifier for treatment for 1-10min, then slowly taking out the galvanized steel substrate, removing redundant liquid by adopting compressed air, cleaning by using absolute ethyl alcohol, and curing to form a film at 80-150 ℃ for 10-40min. The process still has the problem of being complex.
Disclosure of Invention
The invention aims to solve the problems and provides an anticorrosive coating for metal, and preparation and application thereof.
According to the technical scheme of the invention, the anticorrosive paint for the metal comprises the following raw material components in percentage by mass: 80-95% of photo-curing coating precursor and 5-20% of nano particles;
the raw materials of the photo-curing coating precursor comprise a hydrophobic agent, a cross-linking agent and a photoinitiator;
the hydrophobic agent is unsaturated oleate with polyfunctional double bonds;
the cross-linking agent is a mercapto derivative.
The hydrophobic agent can shield direct contact between a corrosive medium and a metal matrix, and a mercapto derivative is used in cooperation with the hydrophobic agent and is used as a basis for curing and film forming; the coating is suitable for use on a variety of metal substrates including, but not limited to, aluminum magnesium alloys and steel.
Further, the mass ratio of the hydrophobic agent, the cross-linking agent and the photoinitiator in the photo-curing coating precursor is 5:2-4:0.5-5.
Further, the unsaturated oleate with multifunctional double bonds is pentaerythritol oleate and/or glycerol oleate.
Furthermore, the mercapto derivative is 3-mercaptopropyltriethoxysilane and/or pentaerythritol tetra-3-mercaptopropionate.
Further, the photoinitiator is photoinitiator 1173.
Further, the nanoparticles are one or more of nano silica, graphene and MXene.
The second aspect of the present invention provides a method for preparing the anticorrosive paint for metal, comprising the following steps,
s1: mixing and uniformly stirring a hydrophobic agent, a cross-linking agent and a photoinitiator, and then carrying out ultraviolet irradiation treatment to obtain a photocuring coating precursor;
s2: and adding the nano particles into the photocureable coating precursor, and uniformly stirring to obtain the anticorrosive coating for the metal.
Further, in the step S1, the ultraviolet irradiation treatment time is 2-8h, and the illumination intensity is 0.5-5mW cm -2 。
Specifically, the preparation method of the anticorrosive paint for metals can be as follows:
s1: the mass ratio of the hydrophobic agent to the cross-linking agent to the photoinitiator is 5:2-4:0.5-5, stirring, and placing under illumination intensity of 0.5-5mW cm -2 Irradiating for 2-8h under an ultraviolet lamp to obtain a photocureable coating precursor;
s2: and (2) adding 5-20 wt% (based on the content of the nanoparticles in the anticorrosive coating for metals) of nanoparticles into the photocureable coating precursor obtained in the step (S1), and uniformly stirring to obtain the anticorrosive coating for metals.
The third aspect of the invention provides an application of the anticorrosive paint for metal in metal corrosion prevention, which is characterized in that the anticorrosive paint for metal is coated on the surface of metal, and an anticorrosive coating is formed after the anticorrosive paint for metal is subjected to heat curing process treatment.
Further, the coating can be carried out by a blade coating method, the coating thickness is 100-500um, specifically, the light and thin coating is less than about 150um, and the thick coating is more than 200 um.
Further, the temperature of the heat curing process is 130-150 ℃, and the time is 8-15min; preferably, the curing is carried out at 140 ℃ for 10min.
Compared with the prior art, the technical scheme of the invention has the following advantages:
1. the anticorrosive coating avoids the use of organic solvents, is simple and environment-friendly, has short flow, is suitable for industrial processing production, and has high utilization rate and excellent anticorrosive performance;
2. besides the anticorrosion performance of the base material, the functional nano particles in the coating can endow the coating with light aging resistance and high temperature resistance, so that the application of the anticorrosion coating in a complex environment is met.
Drawings
FIG. 1 is a PM/SiO coating 2 SEM micrographs of the latter aluminum magnesium alloy AZ 31B.
FIG. 2 is a PM/SiO coating 2 Optical photograph of the water contact angle of the aluminum magnesium alloy AZ 31B.
Fig. 3 is a tafel polarization curve of the aluminum magnesium alloy AZ31B before and after coating.
Table 1 shows tafel polarization parameters of al-mg alloy AZ31B before and after coating.
Fig. 4 is a nyquist curve of aluminum magnesium alloy AZ 31B.
Fig. 5 is a nyquist curve for al-mg alloy AZ31B after PM coating.
FIG. 6 is a PM/SiO coating 2 Nyquist curve of the latter aluminum magnesium alloy AZ 31B.
Fig. 7 is a bode plot of the impedance modulus versus frequency of al-mg alloy AZ31B before and after coating.
Fig. 8 is a phase angle-frequency bode plot of al-mg alloy AZ31B before and after coating.
Detailed Description
The present invention is further described below in conjunction with the following figures and specific examples so that those skilled in the art may better understand the present invention and practice it, but the examples are not intended to limit the present invention.
Example 1
A preparation method and application of an anticorrosive coating for metal comprise the following steps:
(1) Pentaerythritol oleate, 3-mercaptopropyltriethoxysilane and a photoinitiator 1173 are mixed according to the mass ratio of 5:4:1 adding the mixture into a quartz beaker, uniformly stirring the mixture by magnetic force, and then placing the quartz beaker under an ultraviolet lamp source to irradiate the quartz beaker for 4 hours with the illumination intensity of 2.5mW cm -2 And obtaining the photocureable coating precursor.
(2) And (2) mixing the nano silicon dioxide particles into the photo-curing coating precursor prepared in the step (1), wherein the using amount is 5 wt%, and mechanically stirring uniformly to obtain the anticorrosive coating.
(3) Coating an anticorrosive paint on the surface of the alloy (metal), and curing in an oven at 140 ℃ for 10 minutes to form an anticorrosive coating (PM/SiO) on the surface of the alloy 2 )。
Example 2
A preparation method and application of an anticorrosive coating for metal comprise the following steps:
(1) Pentaerythritol oleate, 3-mercaptopropyltriethoxysilane and a photoinitiator 1173 are mixed according to the mass ratio of 5:4:1 adding the mixture into a quartz beaker, uniformly stirring the mixture by magnetic force, and then placing the quartz beaker under an ultraviolet lamp source to irradiate the quartz beaker for 4 hours with the illumination intensity of 2.5mW cm -2 And obtaining the photocureable coating precursor.
(2) And (3) coating the photo-curing coating precursor on the surface of the alloy in a blade mode, and curing for 10 minutes in an oven at the temperature of 140 ℃ to form an anticorrosive coating (PM) on the surface of the alloy.
Example 3
A preparation method and application of an anticorrosive coating for metal comprise the following steps:
(1) Glycerol oleate, pentaerythritol tetra-3-mercaptopropionate and a photoinitiator 1173 are mixed according to the mass ratio of 5:3:2 adding the mixture into a quartz beaker, uniformly stirring the mixture by magnetic force, and then placing the quartz beaker under an ultraviolet lamp source to irradiate the quartz beaker for 4 hours with the illumination intensity of 2.5mW cm -2 And forming a light-cured coating precursor on the surface of the alloy.
(2) And (2) mixing the graphene powder into the photo-curing coating precursor prepared in the step (1), wherein the using amount is 15 wt%, and mechanically stirring uniformly to obtain the anticorrosive coating.
(3) Coating an anticorrosive paint on the surface of the alloy, and curing in an oven at 140 ℃ for 10 minutes to form an anticorrosive coating on the surface of the alloy.
Example 4
A preparation method and application of an anticorrosive coating for metal comprise the following steps:
(1) Pentaerythritol oleate, pentaerythritol tetra-3-mercaptopropionate and a photoinitiator 1173 are mixed according to the mass ratio of 5:2:0.5 is added into a quartz beaker, the mixture is stirred evenly by magnetic force, and then the quartz beaker is placed under an ultraviolet lamp source for irradiation for 4 hours, wherein the illumination intensity is 2.5mW cm -2 And obtaining the photocureable coating precursor.
(2) And (2) mixing the Mxene powder into the photo-curing coating precursor prepared in the step (1), wherein the using amount is 10 wt%, and mechanically stirring uniformly to obtain the anticorrosive coating.
(3) Coating an anticorrosive paint on the surface of the alloy, and curing in an oven at 140 ℃ for 10 minutes to form an anticorrosive coating on the surface of the alloy.
Test example
The corrosion protection coating prepared in example 1 was tested as follows:
1. sample microstructure characterization
PM/SiO by field emission cold field electron microscopy (SEM) 2 The microstructure of the corrosion protection coating is characterized. As a result, as shown in fig. 1, the surface of the aluminum magnesium alloy AZ31B was covered with a dense coating layer, which resulted in its excellent corrosion resistance.
2. Contact Angle testing
PM/SiO by optical contact Angle measuring apparatus (DataPhysics OCA 20) 2 The hydrophobic properties of the corrosion protection coating were tested with a water drop of 6 μ L and at least five positions were taken and averaged. The results are shown in FIG. 2, PM/SiO 2 The water contact angle of the corrosion resistant coating is about 85 deg., which indicates that it is effective to some extent in shielding corrosive media from contact with the substrate.
3. Tafel polarization curve test
The test employed a three-electrode system with silver/silver chloride (3M KCl) and platinum sheet electrodes (10 mm. Times.10 mm. Times.0.1 mm) as the respective electrodesA reference electrode and a counter electrode, and an aluminum magnesium alloy AZ31B (10 mm. Times.10 mm. Times.0.1 mm) before and after coating were fixed on an electrode holder as a working electrode. Before the test, the electrodes were connected but not energized and placed in a sodium chloride electrolyte with a mass concentration of 3.5% for two hours to allow the open circuit potential OCP to reach equilibrium, then at 1mV s -1 Is scanned and the corresponding tafel polarization curve is recorded with the electrochemical workstation RST-5000. The results are shown in FIG. 3 and Table 1 for coatings PM and PM/SiO 2 Thereafter, the corrosion current icorr of the Al-Mg alloy AZ31B was from 1.05X 10 -5 A cm -2 Down to 1.24X 10 -7 A cm -2 /3.12×10 -9 A cm -2 The polarization resistance Rp is 3.89X 10 4 Lifting to 5.12X 10 6 /1.25×10 8 And the PE value and the CR value of the corrosion resistance of the anticorrosive film are respectively as high as 98.79%/99.97% and 2.71 multiplied by 10 -3 μm year-1/6.85×10 -5 μm year -1 This shows that the photo-curable coating precursors PM and nano SiO 2 The particles all contribute to improving their corrosion protection properties.
TABLE 1 Tafel polarization parameters of Al-Mg alloys AZ31B before and after coating
4. Electrochemical impedance spectroscopy test
A similar process is performed to bring the open circuit potential to equilibrium, then at 10 -2 To 10 -5 The frequency range was scanned with an ac amplitude of 10mV and the corresponding electrochemical impedance spectrum was recorded using the electrochemical workstation RST-5000. Generally, the larger the semi-circular diameter of the Nyquist curve, the better the corrosion protection, as shown in FIGS. 4, 5 and 6, the coatings PM and PM/SiO 2 The semi-circular arc diameter of the nyquist curve of the rear aluminum magnesium alloy AZ31B was significantly increased, which indicates the improvement of the corrosion resistance. Further, as shown in the figure7 and FIG. 8, coatings PM and PM/SiO 2 The impedance modulus of the aluminum magnesium alloy AZ31B in a low frequency domain and the phase angle of the aluminum magnesium alloy AZ31B in a high frequency domain are both higher than those of the pure aluminum magnesium alloy AZ31B, which can also show that the corrosion resistance of the aluminum magnesium alloy AZ31B is improved.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Various other modifications and alterations will occur to those skilled in the art upon reading the foregoing description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications of the invention may be made without departing from the scope of the invention.
Claims (10)
1. The anticorrosive paint for the metal is characterized by comprising the following raw material components in percentage by mass: 80-95% of photo-curing coating precursor and 5-20% of nano particles;
the raw materials of the photocureable coating precursor comprise a hydrophobic agent, a cross-linking agent and a photoinitiator;
the hydrophobic agent is unsaturated oleate with polyfunctional double bonds;
the cross-linking agent is a mercapto derivative.
2. The anticorrosive paint for metal of claim 1, wherein the mass ratio of the hydrophobizing agent, the crosslinking agent and the photoinitiator in the photocureable paint precursor is 5:2-4:0.5-5.
3. The anticorrosive coating for metals according to claim 1 or 2, wherein the unsaturated oleate having a polyfunctional double bond is pentaerythritol oleate and/or glycerol oleate.
4. The anticorrosive paint for metal according to claim 1 or 2, wherein the mercapto derivative is 3-mercaptopropyltriethoxysilane and/or pentaerythritol tetrakis-3-mercaptopropionate.
5. The anticorrosive paint for metal according to claim 1 or 2, wherein the photoinitiator is a photoinitiator 1173.
6. The anticorrosive coating for metals of claim 1, wherein the one or more of nanoparticle nanosilica, graphene, and MXene.
7. A method for preparing the anticorrosive paint for metal according to any one of claims 1 to 6, comprising the steps of,
s1: mixing and uniformly stirring a hydrophobic agent, a cross-linking agent and a photoinitiator, and then carrying out ultraviolet irradiation treatment to obtain a photocuring coating precursor;
s2: and adding the nano particles into the photocureable coating precursor, and uniformly stirring to obtain the anticorrosive coating for the metal.
8. The preparation method according to claim 7, wherein in the step S1, the ultraviolet irradiation treatment time is 2 to 8 hours, and the irradiation intensity is 0.5 to 5mW cm -2 。
9. The use of the anticorrosive paint for metals in metal corrosion prevention according to any one of claims 1 to 6, wherein the anticorrosive paint for metals is coated on the surface of the metal and forms an anticorrosive coating after being subjected to a heat curing process.
10. The use according to claim 9, wherein the heat curing process is carried out at a temperature of 130 to 150 ℃ for a period of 8 to 15min.
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| CN102690559A (en) * | 2012-05-24 | 2012-09-26 | 北京国泰瑞华精藻硅特种材料有限公司 | Aqueous heat-insulating anticorrosive paint |
| CN103589281A (en) * | 2013-11-04 | 2014-02-19 | 上海电力学院 | High temperature resistant anticorrosion coating based on graphene and preparation method thereof |
| CN103881494A (en) * | 2012-12-24 | 2014-06-25 | 深圳市嘉达高科产业发展有限公司 | Metal anticorrosion antifouling paint |
| CN112280437A (en) * | 2020-11-13 | 2021-01-29 | 郑州工程技术学院 | Composite graphene anticorrosive paint and preparation method and application thereof |
| CN113214703A (en) * | 2021-05-07 | 2021-08-06 | 苏州大学 | Water-based photocuring super-hydrophobic coating and preparation method and application thereof |
| CN113493621A (en) * | 2021-08-04 | 2021-10-12 | 苏州大学 | Transparent hydrophobic photocureable coating and preparation method thereof |
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2022
- 2022-10-27 CN CN202211329173.9A patent/CN115746649A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102690559A (en) * | 2012-05-24 | 2012-09-26 | 北京国泰瑞华精藻硅特种材料有限公司 | Aqueous heat-insulating anticorrosive paint |
| CN103881494A (en) * | 2012-12-24 | 2014-06-25 | 深圳市嘉达高科产业发展有限公司 | Metal anticorrosion antifouling paint |
| CN103589281A (en) * | 2013-11-04 | 2014-02-19 | 上海电力学院 | High temperature resistant anticorrosion coating based on graphene and preparation method thereof |
| CN112280437A (en) * | 2020-11-13 | 2021-01-29 | 郑州工程技术学院 | Composite graphene anticorrosive paint and preparation method and application thereof |
| CN113214703A (en) * | 2021-05-07 | 2021-08-06 | 苏州大学 | Water-based photocuring super-hydrophobic coating and preparation method and application thereof |
| CN113493621A (en) * | 2021-08-04 | 2021-10-12 | 苏州大学 | Transparent hydrophobic photocureable coating and preparation method thereof |
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