Composite organic NANO superhydrophobic Anti-icing coating and preparation method therefor

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 its preparation method Technical Field

[0001] The present invention relates to the technical field of coatings, and more particularly to a composite organic nano super-hydrophobic anti-icing coating and a preparation method thereof. Background Art

[0002] Icing is formed by a combination of complex weather processes and microphysical processes. When the atmospheric temperature is close to or below 0°C, a white transparent or opaque ice layer formed by low-temperature water or supercooled water is frozen on objects with a temperature close to or below 0°C. Generally, power lines are designed to withstand a certain thickness of icing. When the ice on the conductors exceeds the design standard, accidents such as tower collapse and line breakage may occur. Even slight icing can easily 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 superhydrophobic 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. The waterproof materials commonly used 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 inorganic materials have poor permeability in wires and cables, that is, they are difficult to adhere to their surface.

[0003] Summary of the Invention

[0004] To address the existing problems of excessively high surface free energy in anti-icing materials for wires and cables, as well as the poor permeability of inorganic materials in wires and cables, making them difficult to adhere to, this invention provides a composite low-surface-energy organic nano-superhydrophobic anti-icing coating, a room-temperature curable low-surface-energy anti-icing coating. This invention achieves a superhydrophobic effect by first preparing a low-surface-energy hydrophobic material as a primer; then, adding mesoporous molecular sieves and nano-inorganic fillers to this material creates a micron-nano dual roughness structure.

[0005] 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; and comprises the following components in parts by weight:

[0006] In the preferred embodiment, the following components are included in parts by weight:

[0007] 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.

[0008] 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.

[0009] 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.

[0010] On the other hand, the present invention also provides a method for preparing the 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:

[0011] S1. Mix the organic fluorosilicone rubber, acrylic resin, and thermal sprayed natural basalt powder materials and place them in a blender. Add water and stir at low speed for 1.5 to 2.5 minutes, then at high speed for 2.5 to 3.5 minutes, and then let it stand for 25 to 35 minutes to obtain the primer.

[0012] S2. Add end-hydroxy 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 it stand for 8 to 15 minutes to obtain a composite low surface energy organic nano super-hydrophobic anti-icing coating.

[0013] In a preferred embodiment, the preparation method of the thermal spray natural basalt powder material includes: adding an adjusted oxide to basalt waste material for sintering, cooling, adding a surfactant, crushing, and pulverizing to obtain thermal spray natural basalt powder with a particle size of 30 to 150 μm.

[0014] In a preferred embodiment, the pulverization method is ball milling.

[0015] In a preferred embodiment, the sintering conditions are: under standard atmospheric pressure, a sintering temperature of 1200-1400° C., a sintering time of 5-6 hours; and a cooling time of 4 hours.

[0016] 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.

[0017] 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 act as a "microreactor" to accommodate stable "guest" materials and become "host-guest materials", allowing the resin material to be 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 facilitates the construction of 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 fluorosilicone composite polymer materials, added auxiliary micron-sized inorganic fillers, and formed a micro-nano structure with a "lotus effect", thereby preparing a high-performance anti-icing composite coating for transmission lines, and studied and verified its deicing stress and anti-icing effect.

[0018] The present invention is based on a hydroxyl-containing resin, a composite hydrophobic material, and is cured at room temperature with a curing agent to produce a coating with a nanostructure of a "lotus effect" (a bionic structure on the surface of a lotus leaf) and a self-assembled composite microsurface structure of "surface anisotropy" (a bionic structure on the surface of a duck feather).

[0019] The purpose of the present invention is achieved through the following technical solutions:

[0020] The selection of a matrix requires a comprehensive consideration of its low surface energy, high adhesion strength, and sufficient mechanical strength. Generally, a coating containing a large number of -CH3 and -CF3 groups, distributed on the coating surface, results in a high degree of hydrophobicity. Major domestic and international companies produce various types of hydroxyl-containing resins, including hydroxyl-containing acrylic resins, polyester resins, epoxy resins, and hydroxyl-containing polydimethylsiloxanes. Isocyanate or silane coupling agents are used as curing agents to stabilize the ratio of hydroxyl groups to isocyanate groups and silane coupling agent functional groups. Taking into account hydrophobicity, curing time, weather resistance, and tensile strength, hydroxyl-terminated silicone rubber is selected as the film material. The base rubber is modified with fluorinated small molecules to prepare the coating. The surface of the low-surface-energy hydrophobic material is roughened. After fixing the amount of base rubber in the system, nano-mesoporous molecular sieves MCM41 and MCM48 and fumed silica are added to the system to construct a micro-nanostructure on the paint film surface, thereby achieving superhydrophobicity.

[0021] Variations in curing agent content have a certain impact on curing time, adhesion strength between the paint and metal, and the strength of the paint itself. As the curing agent increases, the curing speed of the paint film increases, affecting the degree of reaction of the final paint film, resulting in significant changes in the film's flexibility and shear strength with the metal.

[0022] 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, and the wear resistance is 0.40-0.60 g / cm 2 , acid resistance: 92-96%, alkali resistance: 93-96%.

[0023] The beneficial effects of the present invention are:

[0024] 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 the coating to have micron-level cracks and agglomerates. 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 periods of rain, 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 hydrophobicity 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, ensuring the anti-icing ability of its coating.

[0025] 2. In the early stage of the development process, the coating system of the present invention is developed based on organic fluorine silicone rubber. Fluorine silicone rubber has unique advantages in properties such as low surface energy, insulation, and weather resistance, but it also has natural disadvantages, that is, poor mechanical properties, which are reflected in hardness and low wear resistance. Therefore, it is necessary to add other materials to reinforce the coating. At present, by combining acrylic resins and other materials to form block copolymers, the physical properties of the material can be effectively improved. Later stages also need to further study how to improve the mechanical properties of the material while ensuring super-hydrophobic micro-nano structure and improve the service life. The present invention successfully prepares a micro-nano structure with a lotus leaf-like structure by organic fluorine silicon materials, nano-mesoporous molecular sieves and inorganic fillers. The surface has super-hydrophobic properties, and 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 agent, optimal filler content and the most suitable curing agent dosage are determined. While ensuring the super-hydrophobic properties of the coating, the physical strength of the coating is ensured and the loss of raw materials is reduced.

[0026] 3. The coating prepared with the coating of the present invention has a much stronger adhesion to metal substrates than to ice, allowing it to effectively adhere to conductors. The de-icing force of the coating is an order of magnitude lower than that of the metal substrate, effectively reducing ice adhesion and facilitating ice removal. After curing, this fluorosilicone material system exhibits excellent chemical stability, is resistant to corrosion and aging, has high thermal stability, and offers excellent UV protection, making it suitable for outdoor environments. The coating also exhibits excellent mechanical properties and is effectively resistant to natural wear.

[0027] 4. In anti-icing performance tests, the coating of the present invention effectively reduced the growth of ice accumulation on flat plate samples in the initial stage under harsh conditions of -2 to -6°C and humidity above 80%. The coating achieved an adhesion rating of Level 1 according to the GB / T9286-1998 test standard and a water contact angle of 105 degrees according to the QB / C0611-2005 standard, demonstrating its anti-icing capabilities. In experiments on conductor anti-icing in freezing rain, the coating effectively reduced ice accumulation on the sample, reduced the adhesion between ice and the conductor, and allowed ice to be removed by gravity and external force in continuous rainfall. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 is a diagram of a hydrophobic lotus leaf;

[0029] Figure 2 is a schematic diagram of an electron microscope scan of water droplets on a lotus leaf;

[0030] Figure 3 is a comparison chart of some properties of various resins;

[0031] Figure 4 shows the effect of nano-mesoporous molecular sieve and filler on contact angle;

[0032] Figure 5 shows the effect of nano-mesoporous molecular sieves and fillers on the rolling angle;

[0033] Figure 6 shows the relationship between the amount of curing agent added and the mechanical properties of the coating;

[0034] Figure 7 shows the relationship between the amount of curing agent added and the hydrophobicity of the coating. DETAILED DESCRIPTION

[0035] This invention uses low-surface-energy polymer materials such as domestically produced organosilicon and fluorosilicone elastomers as a base material, combined with inorganic materials to enhance coating performance, and uses a compounding method to prepare a composite low-surface-energy organic nano-superhydrophobic anti-icing coating. The new material of this invention incorporates mesoporous molecular sieves and nano-inorganic fillers on the basis of superhydrophobic materials, which can solve the adhesion problem and enable the coating to adhere firmly to wires and cables. This will be further explained below with reference to the following examples and accompanying drawings.

[0036] Example 1 Formulation Development Process

[0037] The journal "New Building Materials" in 2017, Issue 10, Pages 128 to 131, explains the basic principles of super-hydrophobic surfaces, uses low-surface-energy materials as primers, constructs super-hydrophobic structures, and demonstrates the relationship between primers and surface structures. The current preparation technology and materials used for super-hydrophobic coatings are summarized, and their application prospects are envisioned. A super-hydrophobic surface requires two conditions: low-surface-energy materials and surface microstructures. The present invention first prepares a low-surface-energy hydrophobic material as a primer; then, mesoporous molecular sieves and nano-inorganic fillers are added to this material to construct a micron-nano dual rough structure, thereby achieving a super-hydrophobic effect.

[0038] Mesoporous molecular sieve materials possess a regularly ordered pore structure and an extremely high specific surface area, providing excellent reaction conditions. The ordered pores within the molecular sieve act as "microreactors," accommodating stable "guest" materials, thereby becoming "host-guest materials," allowing the resin material to be evenly distributed within them, thereby enhancing mechanical properties. Furthermore, the mesoporous molecular sieve materials offer a wide range of selectivity in size, facilitating the construction of micro- and nano-surface structures. Based on these considerations, we physically and chemically compounded materials such as mesoporous molecular sieves with highly hydrophobic and highly hydrophobic organofluorosilicone composite polymers, adding auxiliary micron-sized inorganic fillers to form micro- and nano-structures with a "lotus effect." This resulted in the preparation of a high-performance anti-icing composite coating for power transmission lines. The coating's deicing stress and anti-icing effectiveness were also studied and verified.

[0039] The formulation process is as follows:

[0040] 1. Selection of coating resin system

[0041] Some physiological structures of plants and animals in nature, such as lotus leaves, butterflies, and roses, share a common characteristic: their surfaces have multi-scale rough structures—micro-nano structures. To construct a biomimetic super-hydrophobic surface, both low surface energy and surface roughness must be met simultaneously. There are generally two approaches: one is to generate micro-nano structures 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 approach often requires multiple steps, and many construction methods are complex and costly, making them unsuitable for large-scale applications. Therefore, a method for generating micro-nano structures on a hydrophobic substrate is used to design and manufacture super-hydrophobic coatings.

[0042] Figure 1 shows a hydrophobic lotus leaf, and Figure 2 is an electron micrograph of a water droplet on a lotus leaf. When selecting a substrate, consider its low surface energy, high adhesion strength, and adequate mechanical strength. Generally, coatings containing a high number of -CH3 and -CF3 groups, distributed on the surface, exhibit high hydrophobicity.

[0043] Different types of hydroxyl-containing resins produced by major 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 groups to isocyanate groups and silane coupling agent functional groups. Preliminary screening tests were conducted based on the main technical indicators of the current product enterprise standards. The test results are shown in Table 1.

[0044] Table 1 Performance comparison of various resins

[0045] 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 strength and weather resistance of resins in different systems are different. High-voltage transmission lines are made of aluminum stranded wire, which needs to be exposed to the outdoors for a long time and needs 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. Taking into account the hydrophobicity, curing time, weather resistance, and tensile fracture properties, end-hydroxy silicone rubber was selected as the paint film material, and the base glue was modified with fluorine-containing small molecules to prepare the coating.

[0046] 2. Addition of nano-mesoporous molecular sieves and inorganic fillers

[0047] After determining the base adhesive system, in order to prepare a superhydrophobic coating, it is necessary to roughen the surface of the hydrophobic material with low surface energy. After fixing the amount of base adhesive in the system, we add nano-mesoporous molecular sieves MCM41, MCM48, and fumed silica to the system, with the addition amount of each being 10%-15% of the total amount (the optimal addition amount is 12%), to build a micro-nanostructure on the paint film surface, thereby achieving superhydrophobicity.

[0048] Table 2 Contact angle and shear strength of water on the surface of the material before and after nano-mesoporous molecular sieve composite

[0049] Table 2 shows that the materials containing nano-mesoporous molecular sieves exhibit superior superhydrophobic properties compared to those without nano-mesoporous molecular sieves. This is likely due to the excellent nanoscale dispersion of the nano-mesoporous molecular sieves combined with the fluorosilicone material. Combined with the micron-sized filler, this creates a rich micron-nanostructure on the coating surface, resulting in a "lotus effect"-like micro-nanostructure. This micro / nanostructure reduces the contact area between water and the solid surface, maximizing the contact area between the solid surface and air, resulting in superhydrophobic properties. The MCM48 nano-mesoporous molecular sieve exhibited superior performance compared to the MCM41 nano-mesoporous molecular sieve, likely due to its three-dimensional pores, which allow for better bonding with the fluorosilicone rubber and provide greater isotropy. Furthermore, when forming the coating film, the nano-mesoporous molecular sieve and the fluorosilicone rubber composite form a uniform continuous phase, forming an effective interpenetrating network structure. This interpenetrating network technology can effectively improve the coating's weather resistance and anti-fouling properties. Silicone resins (polysiloxanes) have low surface energy and are widely used in the military, electrical, and rubber industries due to their excellent thermal and oxidative stability, weather resistance, waterproofness, and electrical insulation properties. However, their poor mechanical strength severely restricts their application. The material prepared by the present invention can form an interpenetrating network structure, enabling polymers with different functions to form a stable combination, effectively improving the compatibility of the polymer chains and increasing the network density, thereby compensating for the deficiencies of the individual components and achieving excellent film properties.

[0050] Table 3 Test on the addition amount of nano-mesoporous molecular sieve and nano-inorganic filler

[0051] Figures 4 and 5 show the effects of two filler contents on the contact angle of the coatings. Table 3 shows the data for varying nano-mesoporous sieve and filler content: as the nano-mesoporous sieve and filler content in the system increases from low to high, the contact angle of the paint film increases, remaining essentially constant after reaching a certain 15% content. The rolling angle decreases continuously, remaining essentially constant after reaching 15%. Furthermore, increasing the nano-mesoporous sieve and filler content increases the adhesion between the paint film and the metal. This is because the paint film system contains a high concentration of low-surface-energy materials, which have relatively poor adhesion to the metal. This surface energy difference causes shrinkage during film formation on the metal, affecting the uniformity and smoothness of the final film. The addition of solid fillers increases the viscosity of the paint film to a certain extent and acts as an adsorbent to the surrounding paint film, allowing the curing agent and coupling agent in the paint to form a uniform and smooth film on the metal surface, thus improving adhesion to the substrate. However, excessive amounts of silica can reduce the strength of the paint film, which in turn reduces its adhesion. When the content of nano-mesoporous molecular sieve and filler is further increased 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% as a reasonable value.

[0052] 3. Curing agent addition amount

[0053] 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 cured paint film, the content of the curing agent was adjusted while keeping the base glue and filler content unchanged. The test results are shown in Table 4.

[0054] Table 4 Curing agent addition test

[0055] Combining the effects of different curing agents and their varying dosages on the tensile strength and shear strength of the coatings shown in Figures 6-7, and analyzing the data in Table 4, it can be seen that changes in curing agent content have a certain impact on curing time, adhesion strength between the coating and the metal, and the strength of the coating itself. Increasing the curing agent content increases the curing speed of the paint film and affects the degree of reactivity of the final paint film, resulting in significant changes in the film's flexibility and shear strength against the metal. As can be seen in Table 4, increasing curing agent content increases the shear strength and tensile strength of the coating against the metal after complete curing. Only after reaching a certain level of curing agent can the maximum adhesion between the coating and the metal be achieved. Further increases in curing agent content maintain essentially unchanged adhesion and tensile strength. Therefore, low curing agent content results in incomplete curing of the paint film, resulting in lower physical strength and adhesion; while excessive curing agent content does not further improve the film's performance.

[0056] The effect of changes in curing agent content on the coating's hydrophobicity is not significant and is not a major factor. Generally speaking, when the curing agent content is sufficient to fully crosslink the base glue and other fillers, a stable and strong coating can be formed, resulting in excellent superhydrophobicity. Comprehensively evaluating the results, the table shows that when the curing agent to base glue ratio is 20%, the contact angle is 153° and the rolling angle is 2.8°, indicating that the anti-icing performance is optimal at this ratio. Therefore, the optimal curing agent to base glue ratio was ultimately determined to be 20%.

[0057] Example 2

[0058] A thermal spraying natural basalt powder material contains 70% to 98% natural basalt and 2% to 30% auxiliary component powder (such as additives: chromium oxide, zirconium oxide, or titanium oxide; surfactants: polyethylene glycol, triethanolamine, or phosphate; adjusting oxides: one or more components such as aluminum oxide, iron oxide, titanium oxide, or silicon oxide, with the optimal ratio of basalt to auxiliary components being approximately 5.25:1). The powder is thermally sprayed on a metal substrate to form a high-performance coating.

[0059] Natural basalt powder for thermal spraying can be obtained directly from mineral waste or through sintering, cooling, and subsequent processing. Natural basalt is a basic extrusive rock, primarily composed of calcium-rich clinopyroxene and basic plagioclase; secondary minerals include olivine, orthopyroxene, pyroxene, iron-titanium oxides, alkaline feldspar, quartz or para-feldspar, zeolite, hornblende, mica, apatite, zircon, iron spinel, sulfides, and graphite. The chemical composition of the sprayed basalt powder is primarily composed of SiO2, Al2O3, FeO, CaO, MgO, K2O, and Na2O. Appropriate additives are added to impart good fluidity to the basalt powder.

[0060] If sintering is required during basalt powder preparation, the sintering temperature is 1200-1400°C, carried out under standard atmospheric pressure in a dry environment for 5-6 hours. The powder is then crushed and ball-milled to produce a spray powder with a particle size of 30-150 μm. A thermal sprayer is used to prepare an inorganic coating with an amorphous structure on the metal surface.

[0061] Powder preparation: Use waste materials such as basalt discarded from mines to add the adjusted oxides, and directly crush and pulverize them (such as crushing and ball milling) in the presence of special surfactants to obtain powder with a particle size of 30-150μm. Alternatively, basalt waste can be added to adjust the oxides, and directly crush and pulverize them (such as crushing and ball milling) in the presence of special surfactants, and then sintered, cooled (control the appropriate cooling rate, the cooling time is about 4h), and ground to obtain a powder with a particle size of 30-150μm. The powder has good fluidity and is added with an emulsion resin admixture. The coating thickness is 500-800μm (measured using a 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·℃, and the wear resistance is 0.40-0.60g / cm 2 , acid resistance: 92-96%, alkali resistance: 93-96%.

[0062] 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.

[0063] Example 3

[0064] A composite low surface energy organic nano super-hydrophobic anti-icing coating, the components of which are:

[0065] The preparation steps of a composite low surface energy organic nano super hydrophobic anti-icing coating are as follows:

[0066] Step 1: First, mix the organic fluorosilicone rubber, acrylic resin, and thermal sprayed natural basalt powder material, stir slightly, and then pour it into the blender. Add water and stir at low speed (low speed 30-60r / min) for 2 minutes, then change to high speed (60-120r / min) for 3 minutes, and then let it stand for about 30 minutes to wait for the end-hydroxy silicone rubber, molecular sieve material and inorganic filler to be added.

[0067] The thermal spraying natural basalt powder material can be prepared by any method in Example 2.

[0068] Step 2: Add end-hydroxy silicone rubber to the primer, 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.

[0069] In anti-icing performance tests, under harsh conditions of -2 to -6°C and humidity above 80%, the super-hydrophobic coating on flat samples effectively reduced ice accumulation in the initial stage. Adhesion measured according to the GB / T9286-1998 standard was rated Level 1, and the water contact angle measured according to the QB / C0611-2005 standard was 105 degrees, demonstrating that the coating has some anti-icing capabilities. However, sustained low temperatures and high humidity can degrade or even eliminate anti-icing performance. In anti-icing experiments on conductors under freezing rain conditions, the coating effectively reduced ice accumulation on the samples, weakened the adhesion between ice and the conductors, and allowed ice to detach under both gravity and external forces in continuous rainfall.

[0070] Comparative Example 1

[0071] The components of a domestic hydrophobic coating are:

[0072] The preparation steps of a domestic hydrophobic coating are as follows:

[0073] Step 1: First make the primer. Add acrylic resin, modified polyepoxide and epoxy resin into the mixer in sequence and stir at a slightly low speed (30-60 r / 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. Adjust to high speed and stir for 3 minutes, and then stand for 10-20 minutes.

[0074] Step 2: Add an admixture and 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.

[0075] The coating prepared in Example 3 of the present invention has excellent chemical stability, is not easily corroded or aged, has high thermal stability, and has good UV protection, making it suitable for outdoor environments. The coating also has excellent mechanical properties and is effectively resistant to natural wear. The coating has a thickness of 500-800 μm, a porosity of 1-8%, a microhardness of 800-1600 Hv, a thermal conductivity of 19-24 W / m°C, and a wear resistance of 0.40-0.60 g / cm 2, acid resistance: 92-96%, alkali resistance: 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, ensuring the anti-icing ability of its coating.

[0076] Compared with the coating of Comparative Example 1, the ordinary coating has the characteristics of simple production process and simple materials, good weather resistance and corrosion resistance, can be baked at low temperature, and 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 is easier to combine with moisture, so its anti-icing effect is also very poor. On the other hand, the coating of the present invention also adds natural basalt powder material, which can increase the high temperature resistance, acid and alkali salt resistance, and aging resistance of the coating, thereby enhancing the comprehensive performance of the coating of the present invention.

[0077] In addition, 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 hydrophobicity and anti-icing properties of the coating.

[0078] The above description is only a preferred specific embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any technician familiar with the technical field, within the technical scope disclosed by the present invention, who makes equivalent replacements or changes based on the technical solution and inventive concept of the present invention, should be covered by the scope of protection of the present invention.

Claims

1. A composite organic nano super-hydrophobic anti-icing coating, characterized in that: It includes a gelling material, water and a curing agent; the gelling material includes organic fluorine silicone rubber, acrylic resin, thermal sprayed natural basalt powder material, fumed silica inorganic filler, nano-mesoporous molecular sieve material and hydroxyl-terminated silicone rubber; it includes the following components by weight:

2. The composite organic nano super-hydrophobic anti-icing coating according to claim 1, characterized in that: By weight, it includes the following components:

3. The composite organic nano super-hydrophobic anti-icing coating according to claim 1 or 2, characterized in that: The thermal spraying natural basalt powder material comprises a main material and auxiliary materials, wherein the main material is natural basalt powder, and the auxiliary materials comprise 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.

4. The composite organic nano super-hydrophobic anti-icing coating according to claim 3, 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.

5. The composite organic nano super-hydrophobic anti-icing coating according to claim 3, 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.

6. A method for preparing the composite organic nano super-hydrophobic anti-icing coating according to any one of claims 1 to 5, characterized in that: Adding raw materials according to claim 1 comprises 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.

7. The method for preparing the composite organic nano super-hydrophobic anti-icing coating according to claim 6, characterized in that: The preparation method of the thermal spray natural basalt powder material comprises: adding an adjusted oxide to basalt waste for sintering, cooling, adding a surfactant for crushing, and pulverizing to obtain the thermal spray natural basalt powder with a particle size of 30 to 150 μm.

8. The method for preparing the composite organic nano super-hydrophobic anti-icing coating according to claim 7, characterized in that: The pulverizing method is ball milling.

9. The method for preparing the composite organic nano super-hydrophobic anti-icing coating according to claim 7, characterized in that: The sintering conditions are as follows: 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.

10. The method for preparing the composite organic nano super-hydrophobic anti-icing coating according to claim 6, 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.

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