CN120554919A

CN120554919A - A wear-resistant and corrosion-resistant super-hydrophobic anti-icing coating and its application

Info

Publication number: CN120554919A
Application number: CN202510697846.3A
Authority: CN
Inventors: 贺宗晶; 李卓妍; 穆琛; 楚鸿艳; 马浩; 徐慧宁; 谭忆秋
Original assignee: Harbin Institute of Technology Shenzhen
Current assignee: Harbin Institute of Technology Shenzhen
Priority date: 2025-05-28
Filing date: 2025-05-28
Publication date: 2025-08-29

Abstract

The present invention discloses a wear-resistant, corrosion-resistant super-hydrophobic anti-icing coating and its application, belonging to the field of protective coating technology. The coating is composed of a microscopic skeleton layer and a nanoscopic functional layer, wherein the microscopic skeleton comprises epoxy resin, curing agent, polyaniline and microstructural materials; the nanoscopic functional layer comprises epoxy resin, polydimethylsiloxane, nanoparticles, nano The coating of the present invention has super-hydrophobicity, ice resistance, high wear resistance and long-term corrosion resistance, and is suitable for protecting substrates in high-corrosion and low-temperature icing environments such as marine engineering and industrial equipment.

Description

Wear-resistant and corrosion-resistant super-hydrophobic ice-resistant coating and application thereof

Technical Field

The invention relates to the technical field of protective coatings, in particular to a wear-resistant super-hydrophobic ice-resistant coating with multielement corrosion prevention synergistic enhancement and application thereof, which are suitable for comprehensive protection of metal, composite materials and building base materials in marine and industrial pollution and high-humidity low-temperature environments by the synergistic design of a micro-nano gradient structure and functional components and simultaneously solve the problems of long-acting protection and low-temperature ice condensation in an extreme corrosion environment.

Background

In the industrial and construction fields, the problem of deterioration of material surfaces due to prolonged exposure to corrosive environments (such as salt spray, acid rain, chemical media and low temperature ice condensation) is increasingly pronounced. The traditional anti-corrosion coating technology is designed with multiple focusing and single functions, namely the super-hydrophobic anti-icing coating can block water penetration through a micro-nano structure, but high-concentration nano materials are easy to cause cracks of the coating, the anti-icing performance is insufficient in a low-temperature environment, and the anti-corrosion coating can delay the corrosion of a substrate and can rapidly fail due to insufficient mechanical durability. The existing research shows that the single protection mechanism is difficult to combine long-acting hydrophobicity, corrosion resistance and ice anticoagulation performance. In addition, in the prior art, single nano materials or antiseptic factors are mostly adopted, and multiple collaborative designs are lacked. For example, nano CeO ₂ can inhibit corrosion through passivation, but has poor interfacial compatibility with hydrophobic components, which is easy to cause coating layering, and Carbon Nanotubes (CNTs) can enhance hydrophobicity and photothermal conversion capability, but excessive addition can cause coating brittleness to increase. Therefore, an innovative coating design is needed, and the technical bottlenecks of high hydrophobicity, strong adhesive force, long-acting corrosion resistance and ice-resistant performance are broken through the cooperative optimization of the gradient composite structure and the multiple corrosion resistance factors, so that an efficient and stable solution is provided for substrate protection in extreme environments.

Disclosure of Invention

In view of the defects existing in the prior art, the invention provides a wear-resistant and corrosion-resistant super-hydrophobic ice-resistant coating which is particularly suitable for improving the durability of metals, composite materials and building base materials in extreme environments such as high salt, high humidity, industrial pollution and the like.

The technical aim of the invention is realized by the following technical scheme:

the invention provides a wear-resistant and corrosion-resistant super-hydrophobic ice-resistant coating, which comprises a microcosmic framework layer and a nano functional layer which are sequentially coated on a metal substrate,

As a specific embodiment, the micro skeleton comprises epoxy resin, a curing agent, polyaniline and a microstructure material, wherein the curing agent is at least one selected from Diethylenetriamine (DETA), ethylenediamine (EDA) or triethylenetetramine (TETA);

As a specific embodiment, the nano-functional layer comprises epoxy resin, polydimethylsiloxane (PDMS), nano-particles and nano-particles Polyaniline (GANI).

As a specific embodiment, the microstructure material comprises quartz sand particles, siC particles, silicon carbide particles (SiC) and alumina particlesBoron carbide particlesOr silicon nitride particlesAt least one of them.

As a specific embodiment, the microstructure material has a particle size of 40-60 mesh.

As a specific implementation mode, the microstructure material is uniformly dispersed on the epoxy resin matrix through a screen, and a porous rigid framework is formed after solidification.

As a specific implementation, in the micro skeleton, the ratio of the epoxy resin to the curing agent to the polyaniline is 100:10-20:3-10 in parts by weight.

As a specific embodiment, the nanoparticle is at least one selected from the group consisting of nano SiO ₂, nano TiO ₂, nano Al ₂O₃, carbon nanotube, graphene nanoplatelet, and nanoclay.

In one specific embodiment, the nano-functional layer comprises the epoxy resin, the polydimethylsiloxane, the nano-particles and the nano-particles in parts by weightThe proportion of polyaniline is 100:10-20:100-110:10-20:3-10.

As a specific embodiment, the nano-meterThe particle size of (3) is 20-50 nm.

As a specific embodiment, the nano-meterAfter surface hydroxylation modification, the modified polymer is uniformly dispersed in the nano-functional layer.

The invention further provides application of the wear-resistant anti-corrosion super-hydrophobic gradient composite coating in preparation of anti-corrosion coatings of ocean engineering and industrial equipment.

Compared with the prior art, the invention has the beneficial effects that:

The invention constructs a micro-nano dual coarse structure based on the design and preparation method of the carbon nano tube gradient composite and multi-element anti-corrosion synergistic enhanced super-hydrophobic anti-ice coating, which remarkably delays the formation of ice nuclei and reduces the adhesive force of an ice layer. The coating solves the technical bottleneck that the high hydrophobicity, the strong adhesive force, the long-acting corrosion resistance and the ice resistance are difficult to coexist in the traditional coating through the cooperative optimization of the gradient composite structure and the multiple corrosion resistance factors. The coating disclosed by the invention has superhydrophobic ice resistance, high wear resistance and long-acting corrosion resistance, and is suitable for protecting a substrate in high-corrosion and low-temperature ice condensation environments of ocean engineering, industrial equipment and the like. The method is particularly suitable for improving the durability of metals, composite materials and building base materials in extreme environments such as high salt, high humidity, industrial pollution and the like.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.

Fig. 1 is a contact angle image of example 1 coating specimen 1.

FIG. 2 is a graph of the macro topography of the coating of sample 2 of example 2.

Fig. 3 is a scanning electron micrograph of the coating of example 1, sample 1 and example 2, sample 2.

Fig. 4 is a graph showing the change in contact angle of example 1 coating sample 1 at various rubbing times.

FIG. 5 is a photograph of the coating surface of sample 1 of example 1 prior to tape stripping test.

FIG. 6 is a photograph of the surface of the coating of sample 1 of example 1 after tape stripping.

Fig. 7 is a pencil scratch image of the coating of sample 1 of example 1.

FIG. 8 is a graph showing the macroscopic morphology change of sample 1 coated in example 1 before and after immersion in a 3.5% NaCl solution.

Fig. 9 is a graph of the macroscopic morphology change of sample 1 of the coating of example 1 before and after the salt spray test.

Fig. 10 is a graph showing a freezing process of water droplets in the ice-freezing test of sample 3 of example 9.

Fig. 11 is a graph showing a freezing process of water droplets in the ice-freezing test of sample 2 of example 2.

Detailed Description

The invention is further illustrated by the following examples, which are provided to illustrate the invention and are not to be construed as limiting the scope of the invention, which is defined by the appended claims, along with the detailed description of the preferred embodiments and materials.

The terms "comprising," "having," "including," or "containing" are intended to be open-ended, meaning the elements recited in the invention, but not to exclude other elements.

The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.

In order that the invention may be more readily understood, certain technical and scientific terms are defined below. Unless clearly defined otherwise herein in this document, all other technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.

For the purposes of the following detailed description, it is to be understood that the invention may assume various alternative variations and step sequences, except where expressly specified to the contrary. Furthermore, all numerical expressions used in the specification, such as the amount of an ingredient, should be understood to be modified by the term "about" in all examples except in any operating examples or where otherwise indicated. It should be noted that all percentages given in this specification and the appended claims refer to weight percentages in the total composition unless otherwise indicated.

Thus, before the present invention is described in detail, it is to be understood that this invention is not limited to the particular illustrated system or process parameters, which may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular embodiments of the invention only and is not intended to limit the scope of the invention in any way.

As used herein, the term "contact angle" or "static contact angle" refers to the angle between a static drop of deionized water and a flat horizontal surface at which the drop is located. When the liquid/vapor interface encounters a solid surface, contact is typically measured using a liquid, and the wettability of the solid surface is quantified by the liquid. The higher the contact angle, the greater the hydrophobic interaction between the surface and the liquid. The slip angle or roll-off angle is defined as the angle between the sample surface and the horizontal plane on which the droplet starts to slide off the sample surface under the influence of gravity. If the liquid is fully spread on the surface and forms a film, the contact angle is zero degrees (0 °). As the contact angle increases, the wettability increases and when the contact angle increases to a theoretical maximum of 180 °, the liquid forms a spherical drop on the surface. The term "moisture-proof" is used to describe surfaces having a high resistance to wetting by a particular reference liquid, and "hydrophobic" is a term used to describe anti-wetting surfaces in which the reference liquid is water. The higher the contact angle, the greater the hydrophobic interaction between the surface and the liquid.

As used herein, the term "hydrophobic" is characterized by a contact angle for water of greater than 90 °, which means that a water droplet does not wet a surface.

As used herein, the term "superhydrophobic" refers to a contact angle for deionized water equal to or greater than 150 ° at room temperature, and "self-cleaning" refers to a slip angle of less than 5 °.

As used herein, the term "coating" means a deposited layer applied to some or all of the exposed surfaces of a substrate.

The polydimethylsiloxane PDMS described in the examples was derived from the American Conning 184, the ingredients PDMS and curing agent, in a mixing ratio of 10:1.

Carbon nanotubes CNTs are purchased from carbon-rich graphene technologies Inc. of Suzhou, with an outer diameter of 8-15nm and a length of 10-50 μm >99.9%.

Nano Al ₂O₃ was purchased from Shanghai milin Biochemical technologies Co., ltd, form gamma, 20nm,99.99%.

The nano CeO ₂ particles are purchased from Shanghai Michlin Biochemical technology Co., ltd, and have a spherical shape of 20nm-50nm and 99.5%.

Polyaniline (GANI) was purchased from Shanghai Meilin Biochemical technologies Co.

Example 1

The invention relates to a carbon nano tube gradient composite and multi-element corrosion-resistant synergistically enhanced super-hydrophobic ice-resistant coating, which is prepared by the following steps:

super-hydrophobic ice-resistant coating based on carbon nano tube gradient compounding and multielement corrosion prevention synergistic enhancement:

Microstructure construction

1. 10G of epoxy resin (EP) and 1g of curing agent (DETA) were diluted with 20g of ethanol (EP mass: DETA mass: ethanol mass=10:1:20);

2. Continuously adding 0.3g polyaniline (GANI) powder (polyaniline mass: EP mass=3:100) into the solution of the step 1, and then heating in a water bath and magnetically stirring for 5min (500 rpm, 30 ℃);

3. Immersing the prepared cement matrix material into the solution obtained in the step 2 to obtain a surface bonding layer;

4. Uniformly dispersing 40-60 mesh quartz sand particles (QSMPs) with a certain mass on the surface coated with the EP adhesive layer obtained in the step 3 through a screen, obtaining the composite material with a micro-rough structure, and curing for 5 hours at 45 ℃.

Structure of (II) nanoscopic structure

1. 10GEP, 1g DETA and 1g polydimethylsiloxane PDMS were diluted with 100g ethanol (EP mass: DETA mass: PDMS mass: ethanol mass=10:1:1:100);

2.1 g of carbon nanotube CNTs, 10g of nano Al ₂O_3、 g of nano CeO ₂ and 0.3. 0.3gGANI (CNTs mass: nano Al ₂O₃ mass: ceO ₂ mass: GANI mass: ethanol mass=10:100:10:3:1000) are added into the solution obtained in the step 1, and the mixed solution is magnetically stirred for 30min (300 turns, 30 ℃) to form a uniform super-hydrophobic suspension.

3. Immersing the composite material with the micro-coarse structure serving as a matrix into the super-hydrophobic suspension, curing for 1h at 45 ℃, repeating the step for 3 times, and curing for 3h after the super-hydrophobic suspension is dipped for the third time to obtain the sample 1 with the multi-element anti-corrosion synergistic enhanced super-hydrophobic anti-icing coating.

Example 2 general superhydrophobic coating:

1. 10gEP, 1g DETA and 1g polydimethylsiloxane PDMS (PartA mass: partB mass=10:1) were diluted with 100g ethanol (EP mass: DETA mass: PDMS mass: ethanol mass=10:1:1:100);

2. 12g of nano Al ₂O₃ (nano Al ₂O₃ mass: ethanol mass=12:100) was added to the solution obtained in the step 1, and the mixed solution was magnetically stirred for 30min (300 rpm, 30 ℃) to form a uniform super-hydrophobic suspension.

3. Immersing the prepared copper plate matrix material into the super-hydrophobic suspension, curing for 1h at 45 ℃, repeating the step for 3 times, and curing for 3h after dipping the super-hydrophobic suspension for the third time to obtain a sample 2 with a common super-hydrophobic coating, wherein a macro-morphology diagram is shown in figure 2.

Example 3 wettability verification

The contact angle measurement is carried out on the sample 1 of the embodiment 1 and the sample 2 of the embodiment 2 by adopting a wetting angle measurement instrument, the volume of water drops used for the control test is 0.8 mu L-1 mu L, and the average value of the measured data at 2 different positions of the superhydrophobic surface is taken by the measured value of the contact angle. Calculation of contact angle the contact angle of the coating of sample 1 of example 1 was measured at 153 deg. by contact angle meter self-contained software testing and analysis, as shown in figure 1. Example 2 sample 2 had a coating contact angle of 150.5 °.

Example 3 microscopic morphology observations

Scanning Electron Microscope (SEM) observations of the coating of example 1 sample 1 and the coating of example 2 sample 2, respectively, revealed that the surface of the coating of example 2 sample 2 (fig. 3 b) was relatively smoother, whereas the surface of the coating of example 1 sample 1 (fig. 3 a) was covered with nanoparticles of 20nm, which roughness imparted to the coating with better durability.

Example 4 abrasive paper rub test

A # 800 sandpaper was prepared and placed with its rough surface facing down on the coated side of sample 1 of example 1, a 200g standard weight was placed on the sandpaper, and the sandpaper was pulled by hand at a constant speed to move horizontally on the sample. The complete friction of the coated surface at the position of the sand paper where the weight is positioned is recorded as one friction cycle. And measuring the contact angle change of the super-hydrophobic anti-icing coating after different friction cycles, and evaluating the friction and abrasion resistance of the super-hydrophobic anti-icing coating by taking the contact angle as an evaluation index. The change in contact angle of the coating at different rubbing times is shown in fig. 4. It can be seen from the figure that the contact angle of the coating has better stability and excellent abrasion resistance.

Example 5 adhesion test

To complete the curing of the coating of sample 1 of example 1, 64 square lattices of dimensions 2mm x 2mm were evenly drawn on the surface of the sample using a gripper device, then the scratched chips were removed using a brush, finally a 3M tape was evenly adhered to the small squares, the tape was rapidly detached from the surface of the coating after waiting for 2 minutes, and the adhesion of the superhydrophobic ice-resistant coating was evaluated by the integrity of the paint film in the lattice. Fig. 5 is a photograph of the coating surface of the test piece before the tape peeling test, and fig. 6 is a photograph of the coating surface of the test piece after the tape peeling, showing that the coating surface after the peeling is complete and almost free of defects, and the adhesion grade reaches the highest grade 5B. The super-hydrophobic anti-icing coating has excellent interface bonding performance with the substrate.

EXAMPLE 6 hardness test

The coating of sample 1 of example 1 was scored sequentially from the hardest pencil until the pencil selected did not scratch the coating, and was noted as the hardness of the coating film. Fig. 7 is a scratch image of the coating, showing that the coating of sample 1 did not show any scratches in the 5H pencil test, and the hardness scale reached 5H.

Example 7

Sample 1 of example 1 and sample 2 of example 2 were placed in a NaCl solution with a mass concentration of 3.5%, table 1 below shows the change of contact angle after the coating was immersed for different days, and fig. 8 shows the macroscopic morphology change patterns before and after immersing sample 1, and no significant change in the surface morphology was observed.

TABLE 1 variation of contact angle of coating with immersion time (units: °)

Soaking time (Tian)	Sample 1 coating	Sample 2 coating
			0	153	150.5
5	152.5	146
			10	152.5	Loss of hydrophobicity

EXAMPLE 8 salt spray test

Sample 1 of example 1 was placed in a salt spray test chamber, a salt spray solution was set to 5% NaCl solution by mass, the temperature in the chamber was constant at 35±2 ℃, and a marine high salt spray environment was simulated by continuous spraying. Table 2 below shows the variation of contact angle of the coating after salt spray corrosion, and fig. 9 is a macroscopic comparison of the coating of sample 1 of example 1 before and after the test, and no obvious corrosion points or peeling of the coating were observed on the surface of the coating.

Table 2 sample 1 coating contact angle was varied with the time of salt spray test (units: °)

Test time (hours)	Sample 1 coating
		0	153
5	152.5
		10	149.5
20	152

EXAMPLE 9 anticoagulation test

The procedure of example 1 was repeated except that the substrate in the procedure of example 1 was replaced with a copper plate to obtain a coated sample 3. Anti-icing performance tests were performed on sample 3 and sample 2, respectively, with the cold stage temperature set at-15 ℃. During the freezing process, it was found that the partial position of the coating surface of sample 3 was coagulated over 6-7 minutes (fig. 10), whereas the coating of sample 2 of example 2 (fig. 11) was completely frozen under the same conditions for only 2-2.3 minutes. The icing time of the sample 3 coating was prolonged to 3 times (6.5 min/2.2 min. Apprxeq.3 times) of the normal coating of sample 2, exhibiting significant anti-icing advantages.

Example 10

The procedure of example 1 was followed except that Diethylenetriamine (DETA) was replaced with Ethylenediamine (EDA), and the weight ratio of epoxy resin, curing agent and polyaniline was 100:20:10, to give sample 4.

Example 11

The procedure of example 1 was followed except that Diethylenetriamine (DETA) in example 1 was replaced with triethylenetetramine (TETA), and the weight ratio of epoxy resin, curing agent and polyaniline was 100:20:3, to give sample 5.

Example 12

The quartz sand in example 1 is replaced by alumina particles, and the epoxy resin, the polydimethylsiloxane, the alumina particles and the nanometer are adoptedAnd polyaniline in a weight ratio of 100:20:110:20:10, and the procedure of example 1 was otherwise exactly the same to obtain sample 6.

Example 13

The quartz sand in the example 1 is replaced by boron carbide particles, and the epoxy resin, the polydimethylsiloxane, the boron carbide particles and the nanometer are adoptedAnd polyaniline in a weight ratio of 100:10:100:10:3, and the procedure of example 1 was otherwise exactly the same to obtain sample 7.

The experiments of examples 3 to 9 are repeated on the samples 4 to 7 of examples 10 to 13, and the experimental results are basically consistent with the results of the samples 1 and 3, and have the excellent properties of superhydrophobicity, wear resistance, corrosion resistance, durability, hardness grade reaching 5H, ice condensation resistance and the like.

In the description of the present specification, reference to the term "one embodiment," "some embodiments," "an embodiment," or "a particular embodiment," etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment is included in at least one embodiment of the invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment. Furthermore, the particular features, structures, materials, or characteristics may be combined in any suitable manner in any one or more embodiments. Furthermore, the various embodiments described in this specification, as well as the features of the various embodiments, can be combined and combined by one skilled in the art without contradiction.

The foregoing examples illustrate only a few embodiments of the invention and are described in detail herein without thereby limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims

1. A wear-resistant, corrosion-resistant super-hydrophobic anti-icing coating, characterized in that the coating comprises a microscopic skeleton layer and a nanoscopic functional layer in sequence.

The microscopic skeleton comprises epoxy resin, curing agent, polyaniline and microstructural material; the curing agent is selected from at least one of diethylenetriamine, ethylenediamine or triethylenetetramine;

The nano-functional layer includes epoxy resin, polydimethylsiloxane, nanoparticles, nano and polyaniline.

2. The wear-resistant, corrosion-resistant super-hydrophobic anti-icing coating according to claim 1, wherein the microstructure material comprises at least one of quartz sand particles, silicon carbide particles, aluminum oxide particles, boron carbide particles, or silicon nitride particles.

3. The wear-resistant, corrosion-resistant super-hydrophobic anti-icing coating according to claim 1 or 2, wherein the particle size of the microstructure material is 40-60 mesh.

4. The wear-resistant, corrosion-resistant super-hydrophobic anti-icing coating according to claim 1, wherein the microstructure material is evenly dispersed on the epoxy resin matrix through a screen and forms a porous rigid skeleton after curing.

5. The wear-resistant, corrosion-resistant super-hydrophobic anti-icing coating according to claim 1, wherein in the micro-skeleton, the ratio of the epoxy resin, the curing agent and the polyaniline is 100:10~20:3~10 by weight.

The wear-resistant, corrosion-resistant super-hydrophobic anti-icing coating according to claim 1 , wherein the nanoparticles are selected from at least one of nano-SiO ₂ , nano-TiO ₂ , nano-Al ₂ O ₃ , carbon nanotubes, graphene nanosheets, and nano-clay.

7. The wear-resistant, corrosion-resistant super-hydrophobic anti-icing coating according to claim 1, characterized in that in the nano-functional layer, the epoxy resin, polydimethylsiloxane, nanoparticles, nano and polyaniline in a ratio of 100:10~20:100~110:10~20:3~10.

8. The wear-resistant, corrosion-resistant super-hydrophobic anti-icing coating according to claim 1, characterized in that the nano The particle size is 20-50 nm.

9. The wear-resistant, corrosion-resistant super-hydrophobic anti-icing coating according to claim 1, characterized in that the nano After surface hydroxylation modification, it is evenly dispersed in the nano-functional layer.

10. Application of the wear-resistant, corrosion-resistant, super-hydrophobic gradient composite coating according to claim 1 in the preparation of anti-corrosion coatings for marine engineering and industrial equipment.