WO2025130393A1 - Composite organic nano superhydrophobic anti-icing coating and preparation method therefor - Google Patents

Abstract

Disclosed in the present invention are a composite organic nano superhydrophobic anti-icing coating and a preparation method therefor. The coating comprises a cementitious material, water, and a curing agent; the cementitious material comprises organic fluorosilicone rubber, an acrylic resin, a thermal spraying natural basalt powder material, a fumed silica inorganic filler, a nano mesoporous molecular sieve material and hydroxy terminated silicone rubber; and in parts by weight, the coating comprises the following components: 15-20 parts of organic fluorosilicone rubber; 30 parts of the acrylic resin; 30 parts of the thermal spraying natural basalt powder material; 15-20 parts of the fumed silica inorganic filler; 10-15 parts of the nano mesoporous molecular sieve material; 10 parts of hydroxy terminated silicone rubber; 20-30 parts of water; and 1 part of a silane coupling agent. In an anti-icing performance test, in a severe environment with the temperature of -2 to -6°C and the humidity of 80% or above, in an initial stage, the superhydrophobic coating of a flat sample can effectively reduce the increase of the icing amount, the adhesion measured according to the test standard GB/T 9286-1998 is grade 1, and the water contact angle measured according to the standard QB/C 0611-2005 is 105 degrees, which indicates that the coating has a certain anti-icing capability.

Description

A composite organic nano super-hydrophobic anti-icing coating and preparation method thereof Technical Field

The present invention relates to the technical field of coatings, and more specifically to a composite organic nano super-hydrophobic anti-icing coating and a preparation method thereof.

Background Art

Ice is formed by the combination of complex weather processes and microphysical processes. When the atmospheric temperature is close to or below 0℃, low-temperature water or supercooled water is frozen into a white transparent or opaque ice layer on an object with a temperature close to or below 0℃. Generally, power lines are designed to withstand a certain thickness of ice. When the ice on the conductor exceeds the design standard, accidents such as tower collapse and line breakage may occur. Even if the ice is slightly covered, it is easy to cause dancing failures under the action of wind. In order to overcome the failure of wires and cables caused by environmental icing, a new type of organic nano super-hydrophobic anti-icing coating is used to improve the waterproof performance of the surface of wires and cables to improve the anti-icing ability of power lines. At present, the commonly used waterproof materials in China are mainly inorganic materials such as epoxy glue, polyurea, acrylic resin, etc. These materials have good hydrophobicity, but because the surface free energy of these inorganic materials is too high, the permeability of inorganic materials in wires and cables is poor, that is, it is difficult to adhere to their surface.

Summary of the invention

In order to solve the problem that the surface free energy of the anti-icing material of wires and cables in the prior art is too high, the inorganic material has poor permeability in the wires and cables, and is difficult to adhere to the surface of the wires and cables, the present invention provides a composite low surface energy organic nano super hydrophobic anti-icing coating, that is, a low surface energy anti-icing coating that can be cured at room temperature. The present invention first prepares a low surface energy hydrophobic material as a primer; then adds a mesoporous molecular sieve and a nano inorganic filler to the material to construct a micron-nano double rough structure, thereby achieving a super hydrophobic effect.

In order to achieve the above object, the present invention provides a composite organic nano super-hydrophobic anti-icing coating, comprising a gelling material, water and a curing agent; the gelling material comprises organic fluorosilicone rubber, acrylic resin, thermal sprayed natural basalt powder material, fumed silica inorganic filler, nano-mesoporous molecular sieve material and hydroxyl-terminated silicone rubber; the components are as follows by weight:

In the preferred embodiment, the following components are included by weight:

In a preferred embodiment, the thermal spraying natural basalt powder material includes a main material and auxiliary materials, wherein the main material is natural basalt powder, and the auxiliary materials include additives, surfactants and adjusting oxides; the main material accounts for 70% to 98% of the total mass of the coating, and the auxiliary materials account for 2% to 30% of the total mass of the coating.

In a preferred embodiment, the additive is one of chromium oxide, zirconium oxide and titanium oxide; the surfactant is one of polyethylene glycol, triethanolamine and phosphate; and the adjusting oxide is one or more of aluminum oxide, iron oxide, titanium oxide and silicon oxide.

In a preferred embodiment, the mass ratio of the natural basalt powder to the auxiliary material is 5.25:1, and the mass ratio of the additive, the surfactant and the adjusting oxide in the auxiliary material is 1:3:2.

On the other hand, the present invention also provides a method for preparing a composite organic nano super-hydrophobic anti-icing coating according to any of the above claims, adding raw materials according to any of the above ratios, comprising the following steps:

S1. Mix the organic fluorine silicone rubber, acrylic resin and thermal spray natural basalt powder materials and place them Put it into a mixer, add water and stir at low speed for 1.5-2.5 minutes, then at high speed for 2.5-3.5 minutes, and then let it stand for 25-35 minutes. The primer is obtained;

S2. Add terminal hydroxyl silicone rubber to the base glue, stir at low speed for 25 to 35 seconds, add curing agent and stir at low speed for 0.5 to 1.5 minutes, then add nano-mesoporous molecular sieve material and fumed silica inorganic filler, stir at high speed for 2.5 to 3.5 minutes, and let stand for 8 to 15 minutes to obtain a composite low surface energy organic nano super hydrophobic anti-icing coating.

In a preferred embodiment, the method for preparing the thermal spray natural basalt powder material comprises: adding an adjusted oxide to basalt waste for sintering, cooling, and then adding a surfactant for crushing and pulverizing to obtain a thermal spray natural basalt powder with a particle size of 30 to 150 μm.

In a preferred embodiment, the pulverizing method is ball milling.

In a preferred embodiment, the sintering conditions are: under standard atmospheric pressure, the sintering temperature is 1200-1400° C., the sintering time is 5-6 hours; and the cooling time is 4 hours.

In a preferred embodiment, the low speed in steps S1 to S2 is 30 to 60 r/min, and the high speed is 60 to 120 r/min.

Mesoporous molecular sieve materials have a regular and ordered pore structure and an extremely high specific surface area, providing excellent reaction conditions. The ordered pores in the molecular sieve can be used as a "microreactor" to accommodate stable "guest" materials and become "host-guest materials", so that the resin material is evenly distributed therein, thereby enhancing the mechanical properties. At the same time, the size of the mesoporous molecular sieve material has a wide range of selectivity, which is convenient for constructing micro-nano surface structures. Based on the above considerations, the inventors physically and chemically compounded mesoporous molecular sieves and other materials with highly hydrophobic and highly hydrophobic organic fluorine silicon composite polymer materials, added auxiliary micron-sized inorganic fillers, and formed a micro-nano structure with a "lotus leaf effect", thereby preparing a high-performance anti-icing composite coating for power transmission lines, and studied and verified its deicing stress and anti-icing effect.

The present invention is based on hydroxyl-containing resin, composite hydrophobic material, and uses a curing agent for room temperature curing to produce a coating with a nanostructure of "lotus leaf effect" (bionic structure of lotus leaf surface) and a self-assembled composite micro-surface structure of "surface anisotropy" (bionic structure of duck feather surface).

The objective of the present invention is achieved through the following technical solutions:

The selection of the matrix should comprehensively consider its low surface energy properties, high adhesion strength and certain mechanical strength. Generally, it contains a large number of _-CH3 and _-CF3 groups and is arranged on the surface of the coating, which will produce a higher hydrophobicity. Different types of hydroxyl-containing resins produced by large domestic and foreign companies include hydroxyl-containing acrylic resins, polyester resins, epoxy resins, and hydroxyl-containing polydimethylsiloxanes. Isocyanate or silane coupling agents are used as curing agents to fix the ratio of hydroxyl and isocyanate groups and silane coupling agent functional groups. Considering the hydrophobic properties, curing time, weather resistance, and tensile fracture properties, terminal hydroxyl silicone rubber is selected as the paint film material, and the base glue is modified with fluorine-containing small molecules to prepare the coating. On the surface of the hydrophobic material with low surface energy Roughening treatment: After fixing the amount of base glue in the system, add nano-mesoporous molecular sieves MCM41, MCM48, and fumed silica to the system to construct the micro-nano structure of the paint film surface, thereby achieving super-hydrophobicity of the paint film surface.

The change of curing agent content has a certain influence on the curing time, the adhesion strength between the coating and the metal, and the strength of the coating itself. With the increase of curing agent, the curing speed of the paint film increases to a certain extent, and affects the reaction degree of the final paint film, resulting in a significant change in the flexibility of the paint film and the shear strength between the paint film and the metal.

The coating thickness is 500-800 μm; the porosity is controlled at 1-8%; the microhardness is 800-1600 Hv; the coating thermal conductivity is 19-24 W/m°C, the wear resistance is 0.40-0.60 g/cm ² , the acid resistance is 92-96%, and the alkali resistance is 93-96%.

The beneficial effects of the present invention are:

1. In the early development process, the coating prepared by the coating of the present invention has a macroscopic super-hydrophobic structure, thereby reducing the amount of ice adhesion. However, from a microscopic scale, the uniformity of the coating is not enough. During the curing and drying process of the coating, the agglomeration of nanoparticles and the shrinkage of silica gel will cause micron-level cracks and agglomerates in the coating, and these defects will have an adverse effect on the hydrophobicity of the coating. At present, the coating formula and production process have been improved. The latest research shows that after the improvement, the above-mentioned defects can be reduced by an order of magnitude in quantity and scale, and the uniformity is greatly improved. From the perspective of macroscopic performance, the amount of adhered water (or ice) will be greatly reduced during long-term raining, so that the anti-icing effect is further improved. In the later stage of the present invention, through the modification of inorganic fillers such as nano-mesoporous molecular sieves and fumed silica and the control of the cross-linking polymerization reaction of fluorosilicone rubber, a more uniform micro-nano structure can be further obtained, which can further improve the hydrophobic and anti-icing properties of the coating. At present, the anti-ice and snow coatings commonly used in China include hydrophobic coatings and photothermal coatings, but the anti-icing effect is not ideal. Compared with other coatings, the coating of the present invention has better contact angle and rolling angle (can reach 105 degrees), and the surface energy is lower than 20× ^10-8 N/M, which ensures the anti-icing ability of the coating.

2. In the early development process, the coating system of the present invention was developed based on organic fluorosilicone rubber. Fluorosilicone rubber has unique advantages in low surface energy, insulation, weather resistance and other properties, but it also has natural disadvantages, that is, poor mechanical properties, which are reflected in low hardness and wear resistance. Therefore, other materials need to be added to reinforce the coating. At present, the physical properties of the material can be effectively improved by combining with acrylic resins and the like to form block copolymers. In the later stage, more in-depth research is needed on how to improve the mechanical properties of the material and increase the service life while ensuring the super-hydrophobic micro-nano structure. The present invention successfully prepared a micro-nano structure similar to a lotus leaf by using organic fluorosilicone materials, nano-mesoporous molecular sieves and inorganic fillers. The surface has super-hydrophobic properties, the contact angle can reach more than 150°, and the rolling angle is less than 10°. By adjusting the proportion of inorganic fillers and curing agents, The optimal filler content and the most suitable amount of curing agent were determined, which ensured the super-hydrophobic properties of the coating while ensuring the physical strength of the coating and reducing the loss of raw materials.

3. The coating prepared by the coating of the present invention has a much stronger adhesion to the metal substrate than to ice, and can effectively adhere to the wire. The de-icing tensile force of the coating is one order of magnitude lower than that of the metal substrate, which can effectively reduce the adhesion of ice and facilitate the removal of the ice layer. The fluorosilicone material system has good chemical stability after curing, is not easily corroded and aged, has high thermal stability, good UV resistance, and is suitable for outdoor environments. The coating has good mechanical properties and can effectively resist natural wear.

4. In the anti-icing performance test of the coating of the present invention, in the harsh environment of -2 to -6°C and humidity of more than 80%, in the initial stage, the super-hydrophobic coating of the flat sample can effectively reduce the growth of ice coverage, and the adhesion measured by the test standard GB/T9286-1998 is level 1, and the water contact angle measured in the QB/C0611-2005 standard is 105 degrees, indicating that the coating has a certain anti-icing ability. In the wire anti-icing experiment under freezing rain conditions, the coating can effectively reduce the sample ice coverage, and the adhesion between ice and wire is reduced. In the weather with continuous rainfall, it can be removed by gravity and external force.

BRIEF DESCRIPTION OF THE DRAWINGS

Fig. 1 is a diagram of a hydrophobic lotus leaf;

FIG2 is a schematic diagram of an electron microscope scan of water drops on a lotus leaf;

FIG3 is a comparison chart of some properties of various resins;

FIG4 is the effect of nano-mesoporous molecular sieve and filler on contact angle;

FIG5 is the effect of nano-mesoporous molecular sieve and filler on the rolling angle;

Figure 6 is the relationship between the amount of curing agent added and the mechanical properties of the coating;

Figure 7 shows the relationship between the amount of curing agent added and the hydrophobicity of the coating.

DETAILED DESCRIPTION

The present invention uses low surface energy polymer materials such as domestically produced organosilicon and fluorosilicone elastomer as base materials, combines inorganic materials to enhance coating performance, and adopts a formula compounding method to prepare a composite low surface energy organic nano super hydrophobic anti-icing coating. The new material of the present invention adds mesoporous molecular sieves and nano inorganic fillers on the basis of super hydrophobic materials, which can solve the problem of adhesion and enable the coating to adhere firmly to wires and cables. It will be further described below in conjunction with the embodiments and drawings.

Example 1 Formulation Development Process

The basic principle of super-hydrophobic surface is explained in the journal "New Building Materials" No. 10, 2017, pages 128 to 131. Low surface energy materials are used as base materials to construct super-hydrophobic structures. The relationship between the base material and the surface structure is demonstrated. The current preparation technology and materials used for super hydrophobic coatings are summarized, and their application prospects are prospected. Super hydrophobic surfaces need to meet two conditions, one is low surface energy materials, and the other is surface microstructure. The present invention first prepares a low surface energy hydrophobic material as a base glue; then adds mesoporous molecular sieves and nano inorganic fillers to this material to construct a micron-nano dual rough structure, thereby achieving a super hydrophobic effect.

Mesoporous molecular sieve materials have regular and ordered pore structures and extremely high specific surface areas, providing good reaction conditions. The ordered pores in the molecular sieve can be used as "microreactors" to accommodate stable "guest" materials and become "host-guest materials", so that the resin material is evenly distributed in it, achieving the purpose of enhancing mechanical properties. At the same time, the size of mesoporous molecular sieve materials has a wide range of selectivity, which is convenient for constructing micro-nano surface structures. Based on the above considerations, we physically and chemically compounded mesoporous molecular sieves and other materials with highly hydrophobic and highly hydrophobic organic fluorine-silicon composite polymer materials, added auxiliary micron-sized inorganic fillers, and formed a micro-nano structure with a "lotus leaf effect", thereby preparing high-performance anti-icing composite coatings for transmission lines, and studied and verified its deicing stress and anti-icing effect.

The formulation process is as follows:

1. Selection of coating resin system

Some physiological structures of plants and animals in nature, such as lotus leaves, butterflies, and roses, have a common feature that their surfaces have multi-scale rough structures - micro-nano structures. To construct a bionic super-hydrophobic surface, it is necessary to simultaneously meet the two factors of low surface energy and surface roughness. There are usually two methods: one is to generate a micro-nano structure on a hydrophobic substrate; the other is to chemically modify the surface of the micro-nano structure with a low surface energy substance. The second method mostly requires multiple steps to complete, and many construction methods are complicated to operate and costly, which is not conducive to a large number of applications. Therefore, a method of generating a micro-nano structure on a hydrophobic substrate is used to design and manufacture a super-hydrophobic coating.

Figure 1 is a hydrophobic lotus leaf, and Figure 2 is a schematic diagram of a water droplet on a lotus leaf. The selection of the substrate should comprehensively consider its low surface energy properties, high adhesion strength and certain mechanical strength. Generally, a large number of -CH ₃ and -CF ₃ groups are arranged on the coating surface, which will produce a higher hydrophobicity.

Different types of hydroxyl-containing resins produced by large domestic and foreign companies, including hydroxyl-containing acrylic resins, polyester resins, epoxy resins, and hydroxyl-containing polydimethylsiloxanes, use isocyanate or silane coupling agents as curing agents to fix the ratio of hydroxyl and isocyanate groups and silane coupling agent functional groups. Preliminary screening tests are carried out according to the main technical indicators of the current product enterprise standards. The test results are shown in Table 1.

Table 1 Performance comparison of various resins

As shown in Figure 3, the tensile strength, elongation at break and contact angle results of various resins are shown. By analyzing the data of different resin systems in Table 1, it can be seen that the curing time and performance of different types of paint films have their own characteristics, but the hydrophobicity, tensile resistance and weather resistance of resins in different systems are different. High-voltage transmission lines are aluminum stranded wires, which need to be exposed outdoors for a long time and need to have certain tensile strength and weather resistance. And considering the particularity of outdoor high-altitude construction, it is necessary to use materials with relatively short curing time, long-term stable existence outdoors, and certain tensile properties. In addition, the biggest feature of anti-icing coatings is super hydrophobicity, so hydrophobicity is the focus of our investigation. Considering the hydrophobicity, curing time, weather resistance, and tensile fracture performance, end-hydroxy silicone rubber is selected as the paint film material, and the base glue is modified with fluorine-containing small molecules to prepare the coating.

2. Addition of nano-mesoporous molecular sieves and inorganic fillers

After determining the base glue system, in order to prepare a super-hydrophobic coating, it is necessary to roughen the surface of the hydrophobic material with low surface energy. After fixing the amount of base glue in the system, we added nano-mesoporous molecular sieves MCM41, MCM48, and fumed silica to the system, with the addition amount of 10%-15% of the total amount (the optimal amount is 12%) to construct the micro-nano structure of the paint film surface, thereby achieving super-hydrophobicity on the paint film surface.

Table 2 Contact angle and shear strength of water on the surface of the material before and after nano-mesoporous molecular sieve composite

As can be seen from Table 2, compared with the material without adding nano-mesoporous molecular sieve, the material shows excellent super-hydrophobic properties after adding nano-mesoporous molecular sieve. This may be due to the fact that the composite of nano-mesoporous molecular sieve and fluorosilicone material makes the mesoporous molecular sieve have good dispersibility at the nanoscale, and combined with micron-scale fillers, a rich micron-nano level fluctuation is formed on the surface of the coating. Such a structure makes the coating surface form a micro-nano structure with a "lotus effect". This micro/nano structure reduces the contact area between water and the solid surface, and maximizes the contact area between the solid surface of the material and the air, so that the coating surface has super-hydrophobic properties. The MCM48 nano-mesoporous molecular sieve shows better performance than the MCM41 nano-mesoporous molecular sieve, which may be due to the fact that the MCM48 nano-mesoporous molecular sieve has a three-dimensional stereoscopic channel, which can better combine with fluorosilicone rubber and has better isotropy. On the other hand, when forming a coating film, the fluorosilicone rubber composited with the nano-mesoporous molecular sieve forms a uniform continuous phase and an effective interpenetrating network structure. Interpenetrating network technology can effectively improve the weather resistance and anti-fouling ability of the coating. Organic silicon resin (polysiloxane) has a relatively low surface energy. Due to its good thermal stability and oxidation stability, weather resistance, waterproof and electrical insulation properties, organic silicon resin and modified resin products thereof are widely used in military, electrical and rubber industries. However, its mechanical strength is relatively poor, which seriously restricts its application range. The material prepared by the present invention can form a network interpenetrating structure, which can make polymers with different functions form a stable combination, effectively improve the compatibility of polymer chains and increase network density, thereby making up for the defects of each component and achieving excellent coating performance.

Table 3 Experimental addition amount of nano-mesoporous molecular sieve and nano-inorganic filler

Figures 4 and 5 show the effect of two filler contents on the contact angle of the coating, and the data of the change of nano-mesoporous molecular sieve and filler content in Table 3 show that: when the nano-mesoporous molecular sieve and filler content in the system increases from low to high, the contact angle of the paint film increases, and after reaching a certain 15% content, it remains basically unchanged; the rolling angle continues to decrease, and after reaching 15% content, it remains basically unchanged. At the same time, the increase in the content of nano-mesoporous molecular sieve and filler increases the adhesion between the paint film and the metal. This is because the paint film system contains more low surface energy materials, and the bonding force between the metal and the metal is relatively poor. When the film is formed on the metal, it will shrink due to the difference in surface energy, affecting the uniformity and flatness of the final paint film. The addition of solid fillers increases the viscosity of the paint film to a certain extent, and at the same time has the effect of adsorption and fixation on the surrounding paint film, so that the curing agent and coupling agent in the paint can form a uniform and smooth paint film on the metal surface, which increases the bonding force with the substrate to a certain extent. However, excessive white carbon black will cause the strength of the paint film to decrease, and the bonding force will decrease accordingly. When the content of nano-mesoporous molecular sieve and filler continues to increase to 20%, the content is too high, resulting in cracks in the paint film. Therefore, the addition amount of nano-mesoporous molecular sieve and filler is about 15%, which is a reasonable value.

3. Curing agent addition amount

After determining the content of nano-mesoporous molecular sieve and filler, in order to optimize the curing time of the coating and the performance of the paint film after curing, the content of the curing agent was adjusted while keeping the content of the base glue and filler unchanged. The test results are shown in Table 4.

Table 4 Curing agent addition test

Combined with the effects of different curing agents and their different dosages on the tensile strength and shear strength of the coating with metal shown in Figures 6 and 7, and analyzing the data in Table 4, it can be seen that changes in the curing agent content have a certain impact on the curing time, the adhesion strength between the coating and the metal, and the strength of the coating itself. With the increase of curing agent, the curing speed of the paint film increases to a certain extent, and affects the reaction degree of the final paint film, resulting in a large change in the flexibility of the paint film and the shear strength with the metal. It can be seen from Table 4 that with the increase of curing agent content, the shear strength and tensile strength between the coating and the metal continue to increase after the coating is fully cured. Only when the curing agent reaches a certain amount can the maximum bonding force between the coating and the metal be achieved; continue to increase the curing agent. After the curing agent content is reduced, the bonding force and tensile strength between the paint film and the metal remain basically unchanged. Therefore, if the curing agent content is too low, the paint film will not be fully cured, and the physical strength and bonding force will be low; if the curing agent content is too high, the paint film performance will not be further improved.

The change in curing agent content does not have a significant effect on the hydrophobicity of the coating and is not a major factor. In general, when the curing agent content is sufficient to allow the base glue and other fillers to fully cross-link, a stable and strong coating can be formed, which can produce good super-hydrophobicity. Comprehensively judging from the table, it can be seen that when the ratio of curing agent to base glue is 20%, the contact angle is 153° and the rolling angle is 2.8°, which shows that the anti-icing performance under this ratio is optimal, so the optimal curing agent and base glue ratio was finally determined to be 20%.

Example 2

A thermal spraying natural basalt powder material contains 70% to 98% natural basalt and 2% to 30% auxiliary component (such as additives: chromium oxide, zirconium oxide, or titanium oxide; surfactant: polyethylene glycol, or triethanolamine, or phosphate; adjusting oxide: one or more components such as aluminum oxide, iron oxide, titanium oxide, or silicon oxide, and the optimal ratio of basalt to auxiliary components is about 5.25:1) powder, and a method for thermally spraying the powder on a metal substrate to form a high-performance coating.

Thermal spraying natural basalt powder material can be directly processed from mineral waste, or it can be obtained by sintering, cooling and then processing. Natural basalt is a basic extrusive rock, the main minerals are calcium-rich monoclinic pyroxene and basic plagioclase; secondary minerals are olivine, orthopyroxene, pyroxene, iron-titanium oxide, alkaline feldspar, quartz or para-feldspar, zeolite, amphibole, mica, apatite, zircon, iron spinel, sulfide and graphite. The chemical composition of the _sprayed basalt powder is mainly _SiO2 , _Al2O3 , FeO, CaO, MgO, _K2O , _Na2O , etc., and appropriate additives are added to make the basalt powder have good fluidity.

If sintering is required during the preparation of basalt powder, the sintering temperature is 1200-1400℃, carried out under standard atmospheric pressure, and the air environment is preferably dry, the sintering time is 5-6h, and then crushed and ball-milled to prepare a spray powder with a particle size of 30-150μm. A thermal spray machine is used to prepare an inorganic coating with amorphous as the main structure on the metal surface.

Powder preparation: Use waste materials such as basalt abandoned from mines to add adjustment oxides, and directly crush and pulverize them (such as crushing and ball milling, etc.) in the presence of special surfactants to obtain powders with a particle size of 30-150μm. You can also use basalt waste to add adjustment oxides, and directly crush and pulverize them (such as crushing and ball milling, etc.) in the presence of special surfactants, and then sinter, cool (control the appropriate cooling speed, the cooling time is about 4h), and grind to obtain powders with a particle size of 30-150μm. The powder has good fluidity and adds emulsion resin additives. The coating thickness is 500-800μm (measured by coating thickness gauge PD-CT5). The porosity is controlled at 1-8%. The microhardness is 800-1600Hv. The thermal conductivity of the coating is 19-24W/m·℃, wear resistance: 0.40-0.60g/ ^cm2 , acid resistance: 92-96%, alkali resistance: 93-96%.

During the preparation process, preferably, the additive accounts for 2% to 5% of the total mass of the coating, the surfactant accounts for 6% to 15% of the total mass of the coating, and the adjusting oxide accounts for 4% to 10% of the total mass of the coating; more preferably, the mass ratio of the natural basalt powder to the auxiliary material is 5.25:1, and the mass ratio of the additive, the surfactant and the adjusting oxide in the auxiliary material is 1:3:2.

Example 3

A composite low surface energy organic nano super hydrophobic anti-icing coating, the components of which are:

The preparation steps of a composite low surface energy organic nano super hydrophobic anti-icing coating are as follows:

Step 1: First, mix the organic fluorosilicone rubber, acrylic resin, and thermal sprayed natural basalt powder materials, stir them slightly, and then pour them into the mixer. Add water and stir at a low speed (30-60r/min) for 2 minutes, then change to a high speed (60-120r/min) for 3 minutes, and then let it stand for about 30 minutes to wait for the end hydroxyl silicone rubber, molecular sieve material and inorganic filler to be added.

The thermal spraying natural basalt powder material can be prepared by any method in Example 2.

Step 2: Add end-hydroxy silicone rubber to the base glue, stir slightly at a low speed (30-60 r/min) for 30 seconds, add curing agent and stir at a low speed for 1 minute, then add nano-mesoporous molecular sieve material and fumed silica inorganic filler, stir at a high speed for 3 minutes, so as to construct a micro-nano structure on the surface of the paint film and achieve super-hydrophobicity on the surface of the paint film. Finally, let it stand for 10 minutes to obtain a composite low surface energy organic nano-super-hydrophobic anti-icing coating.

In the anti-icing performance test, in the harsh environment of -2 to -6°C and humidity above 80%, in the initial stage, the super-hydrophobic coating of the flat sample can effectively reduce the growth of ice coverage, and the adhesion measured by the test standard GB/T9286-1998 is level 1, and the water contact angle measured by the QB/C0611-2005 standard is 105 degrees. This shows that the coating has a certain anti-icing ability. However, continuous low temperature and high humidity weather will reduce or even lose the anti-icing performance. In the wire anti-icing experiment under freezing rain conditions, the coating can effectively reduce the amount of ice on the sample, reduce the adhesion between ice and wire, and can be removed by gravity and external force in continuous rainfall.

Comparative Example 1

The components of a domestic hydrophobic coating are:

The preparation steps of a domestic hydrophobic coating are as follows:

Step 1: Prepare the primer first. Add acrylic resin, modified polyepoxide and epoxy resin into the mixer in order and stir at a slightly low speed (30-60r/min) for 30 seconds. Then add titanium dioxide and stir at a low speed for 4 minutes. After standing for 5 minutes, add dodecanedioic acid and stir at a low speed for 1 minute. Stir at a high speed for 3 minutes and then stand for 10-20 minutes.

Step 2: Add an admixture and a leveling agent to the base glue, stir at a low speed for 2 minutes, and let it stand for 1 hour to obtain the hydrophobic coating.

The coating prepared in Example 3 of the present invention has good chemical stability, is not easily corroded and aged, has high thermal stability, good UV resistance, is suitable for outdoor environments, has good mechanical properties, and can effectively resist natural wear. The coating thickness is 500-800μm; the porosity is controlled at 1-8%; the microhardness is 800-1600Hv; the coating thermal conductivity is 19-24W/m℃, the wear resistance is 0.40-0.60g/ ^cm2 , the acid resistance is 92-96%, and the alkali resistance is 93-96%. Compared with other coatings, the coating of the present invention has better contact angle and rolling angle (can reach 105 degrees), and the surface energy is lower than 20× ^10-8 N/M, which ensures the anti-icing ability of the coating.

Compared with the coating of comparative example 1, the common coating has the characteristics of simple manufacturing process and simple materials, good weather resistance and corrosion resistance, can be baked at low temperature, and has good hardness and stain resistance. However, compared with the coating of the present invention, its hydrophobicity is ordinary, the contact angle can only reach 85°, and the surface energy is 12×10 ^-7 N/M, which is easier to combine with water, so its anti-icing effect is also poor. On the other hand, the coating of the present invention also adds natural Basalt powder material can increase the high temperature resistance, acid and alkali resistance, salt resistance, aging resistance and other characteristics of the coating, thereby enhancing the comprehensive performance of the coating of the present invention.

Furthermore, the mesoporous molecular sieve material added to the coating of the present invention has the purpose of enhancing mechanical properties. Through the modification of inorganic fillers such as nano-mesoporous molecular sieves and fumed silica and the control of the cross-linking polymerization reaction of fluorosilicone rubber, a more uniform micro-nano structure can be further obtained, thereby further improving the hydrophobic and anti-icing properties of the coating.

The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims (10)

A composite organic nano super-hydrophobic anti-icing coating, characterized in that it comprises a gelling material, water and a curing agent; the gelling material comprises organic fluorosilicone rubber, acrylic resin, thermal sprayed natural basalt powder material, fumed silica inorganic filler, nano-mesoporous molecular sieve material and hydroxyl-terminated silicone rubber; and comprises the following components by weight:
The composite organic nano super-hydrophobic anti-icing coating according to claim 1 is characterized in that it comprises the following components in parts by weight:
According to claim 1 or 2, the composite organic nano super-hydrophobic anti-icing coating is characterized in that the thermal sprayed natural basalt powder material includes a main material and an auxiliary material, the main material is natural basalt powder, and the auxiliary material includes additives, surfactants and adjustment oxides; the main material accounts for 1.5% of the total mass of the coating. The auxiliary materials account for 70% to 98% of the total mass of the coating, and the auxiliary materials account for 2% to 30% of the total mass of the coating. According to the composite organic nano super-hydrophobic anti-icing coating of claim 3, it is characterized in that the additive is one of chromium oxide, zirconium oxide and titanium oxide; the surfactant is one of polyethylene glycol, triethanolamine and phosphate; the adjusting oxide is one or more of aluminum oxide, iron oxide, titanium oxide and silicon oxide. According to the composite organic nano super-hydrophobic anti-icing coating of claim 3, it is characterized in that the mass ratio of the natural basalt powder to the auxiliary material is 5.25:1, and the mass ratio of the additive, the surfactant and the adjusting oxide in the auxiliary material is 1:3:2. A method for preparing a composite organic nano super-hydrophobic anti-icing coating according to any one of claims 1 to 5, characterized in that raw materials are added according to claim 1, comprising the following steps: S1. Mix the organic fluorosilicone rubber, acrylic resin and thermal sprayed natural basalt powder materials and put them into a mixer. Add water and stir at a low speed for 1.5 to 2.5 minutes, then at a high speed for 2.5 to 3.5 minutes, and then let it stand for 25 to 35 minutes to obtain the primer. S2. Add terminal hydroxyl silicone rubber to the base glue, stir at low speed for 25 to 35 seconds, add curing agent and stir at low speed for 0.5 to 1.5 minutes, then add nano-mesoporous molecular sieve material and fumed silica inorganic filler, stir at high speed for 2.5 to 3.5 minutes, and let stand for 8 to 15 minutes to obtain a composite low surface energy organic nano super hydrophobic anti-icing coating. According to the preparation method of the composite organic nano super-hydrophobic anti-icing coating according to claim 6, it is characterized in that the preparation method of the thermal spraying natural basalt powder material comprises: adding an adjusted oxide to the basalt waste for sintering, cooling, and then adding a surfactant for crushing and pulverizing to obtain a thermal spraying natural basalt powder with a particle size of 30 to 150 μm. The method for preparing the composite organic nano super-hydrophobic anti-icing coating according to claim 7 is characterized in that the pulverizing method is ball milling. According to the preparation method of the composite organic nano super-hydrophobic anti-icing coating according to claim 7, it is characterized in that the sintering conditions are at standard atmospheric pressure, the sintering temperature is 1200-1400°C, and the sintering time is 5-6h; the cooling time is 4h. The method for preparing a composite organic nano super-hydrophobic anti-icing coating according to claim 6 is characterized in that the low speed in steps S1 to S2 is 30 to 60 r/min, and the high speed is 60 to 120 r/min.