Preparation method of super-hydrophobic photo-thermal deicing iron-based amorphous-organic composite coating

Abstract

The invention relates to the technical field of amorphous material surface engineering, in particular to a preparation method of a super-hydrophobic photo-thermal deicing iron-based amorphous-organic composite coating. The method comprises the following steps that S1, a hypersonic flame method is adopted for conducting multi-pass spraying to prepare an iron-based amorphous alloy coating with protrusions with a certain thickness on the surface; s2, preparing an organic super-hydrophobic self-heating coating; and S3, the iron-based amorphous alloy coating with the protrusions with the certain thickness on the surface is evenly coated with the organic super-hydrophobic self-heating coating, and curing treatment is carried out. The corrosion resistance of the prepared composite coating is superior to that of an original iron-based amorphous alloy coating, the surface of the metal coating is endowed with the functional characteristics of super-hydrophobicity and self-heating deicing, the anti-fouling and anti-icing performance of the surface of the metal coating is improved, and meanwhile the service life of the anti-icing coating is prolonged; according to the composite coating, the organic layers and the metal layers are embedded in a staggered mode, so that after the surface of the coating is damaged, the effective super-hydrophobic self-heating deicing function and the high corrosion resistance are still kept.

Description

Technical Field

[0001] The present invention relates to the technical field of amorphous material surface engineering, and in particular to a method for preparing a super-hydrophobic photothermal deicing iron-based amorphous-organic composite coating. Background Art

[0002] In low temperature or high humidity environments, components such as aircraft wings, ship decks, and radar equipment are prone to serious safety accidents due to icing. Currently, the common de-icing methods are active and passive. Active de-icing methods mainly include thermal de-icing and mechanical de-icing. The former consumes a lot of energy and has limited application scenarios; the latter is prone to damage to the surface of the equipment. Passive de-icing methods mainly rely on low-surface-energy coatings to reduce ice adhesion, do not require additional energy input, and are environmentally friendly. However, these coatings (mostly organic materials) can often only delay icing, and the coating surface is prone to wetting state changes under high humidity or mechanical impact, resulting in failure of anti-icing performance. In addition, the coating has a short service life and is easily reduced in coating integrity due to various types of damage. Therefore, there is an urgent need to develop coating materials that have both anti-icing and de-icing functions and long-term protection.

[0003] Iron-based amorphous alloy coatings, due to their unique amorphous structure, offer significant advantages in aviation, marine, and other fields. This material possesses a long-range disordered atomic arrangement and lacks defects such as grain boundaries and dislocations. This gives it high hardness (approximately 800-1000 Hv) and excellent wear resistance, making it particularly suitable for repairing aircraft parts and surfaces susceptible to wear, such as ship decks. Iron-based amorphous alloy coatings, produced using high velocity oxygen fuel (HVAF) technology, have a porosity of less than 1% and a bond strength of 44.1 MPa, offering corrosion resistance far superior to that of traditional steel. These properties make them ideal for critical protective materials in extreme environments. However, in low-temperature, high-humidity environments, the surface of iron-based amorphous alloy coatings exhibits poor hydrophobicity, allowing liquid water to adhere to the coating and nucleate into ice. Ice accumulation on the surface can alter the shape of workpieces and reduce work efficiency. Ice accumulation on offshore platforms can also create inconvenience and danger during operations. Therefore, improving the anti-icing and de-icing properties of iron-based amorphous alloy coatings is crucial.

[0004] Perfluorodecyltriethoxysilane (FAS) has extremely low surface energy and can significantly reduce the contact angle of the material surface, giving the surface super-hydrophobic properties, thereby effectively preventing water droplets from spreading and freezing on the surface. Nano-silica and carbon black materials (such as graphene, carbon nanotubes, etc.) can construct micro-nano structures, which can not only further enhance the super-hydrophobic properties, but also assist in achieving anti-icing and de-icing functions through photothermal effects. The introduction of photothermal conversion materials breaks the limitation that low-surface-energy organic materials can only passively de-ice, but are powerless against already frozen surfaces. However, there is still an unresolved problem, that is, the durability of such coatings is still poor and they are easily ineffective due to external friction or chemical corrosion. Therefore, how to maintain the anti-icing and de-icing effect of the organic layer for a long time is a key issue that needs to be solved urgently in the process of industrial application.

[0005] The high hardness and wear resistance of iron-based amorphous materials provide mechanical support for the coating, and their dense structure blocks the penetration of corrosive media, providing good corrosion resistance. The superhydrophobic component reduces ice adhesion through its micro-nanostructure, and combined with its self-heating function, it can effectively reduce water droplet adhesion and prevent ice formation. Therefore, combining iron-based amorphous alloys with organic superhydrophobic self-heating materials can achieve multifunctional synergy and is of great significance for the development of a coating material that combines anti-icing and de-icing functions with long-term protection. Summary of the Invention

[0006] The purpose of the present invention is to develop a coating material that has both anti-icing and deicing functions and long-term protection. The present invention proposes a method for preparing a super-hydrophobic photothermal deicing iron-based amorphous-organic composite coating.

[0007] The principle of the method described in the present invention is that by compounding an iron-based amorphous alloy with an organic super-hydrophobic self-heating material, an active and passive anti-icing and de-icing function is achieved while giving the anti-icing coating a longer service life. The main principle is to use the iron-based amorphous alloy coating with a surface texture as the "skeleton" of the composite coating to provide mechanical support, and the raised peaks can serve as evenly distributed wear-resistant sites; the organic super-hydrophobic self-heating coating is filled in the depressions of the iron-based amorphous alloy coating substrate to provide the coating with anti-icing and de-icing functions. The two together form a mosaic structure. This structure not only increases the actual contact area between the organic layer and the metal layer, making the bond between the two more firm, but also enables the composite coating to still maintain a certain percentage of anti-icing and de-icing material per unit area after being damaged. Therefore, the new super-hydrophobic self-heating and de-icing iron-based amorphous-organic composite coating described in the present invention is a coating material that has both anti-icing and de-icing functions and long-term protection.

[0008] The present invention provides a method for preparing a super-hydrophobic photothermal deicing iron-based amorphous-organic composite coating, the method comprising the following steps:

[0009] (1) A multi-pass spraying method is used to prepare an iron-based amorphous alloy coating with a certain thickness of protrusions on the surface. The first 1-5 passes are directly sprayed on the upper surface of the substrate, and the spraying thickness is 30-200 μm. In the subsequent 3-5 passes, a screen plate is added between the coating and the spray gun to obtain an iron-based amorphous alloy coating with a certain thickness of protrusions on the surface; the protrusions are evenly distributed, and the coating thickness at the protrusions is increased by 150-300 μm compared with the spraying thickness before the screen plate is added. The projected area of ​​each protrusion is 0.04-0.5 mm 2 , the area of ​​the protrusions per square meter accounts for 25% to 60%; the sieve plate is a thin plate with holes that are consistent with the profile and distribution of the protrusions;

[0010] (2) Prepare organic super-hydrophobic self-heating coating:

[0011] A mixture of three components is prepared: Component A: a mixture of a micro-nanostructured particle material and a photothermal conversion material; Component B: a low-surface-energy organic material that provides flexibility; and Component C: an organic binder.

[0012] Prepare a low surface energy organic material solution that provides super hydrophobic effect: take the low surface energy organic material in an organic solvent and evenly disperse it;

[0013] The above-mentioned component A, component B and component C are mixed and added to an organic solvent and uniformly dispersed, and an appropriate amount of a low surface energy organic material solution providing a super-hydrophobic effect is dropped, and an organic super-hydrophobic self-heating coating is obtained after uniform dispersion, wherein the mass ratio of the organic super-hydrophobic self-heating coating component A, component B, component C and the organic solvent is 1-2:2-3:1-2:30-50;

[0014] (3) The organic super-hydrophobic self-heating coating obtained in step (2) is evenly coated on the iron-based amorphous alloy coating with a certain thickness of protrusions on the surface prepared in step (1), and cured.

[0015] Furthermore, the supersonic flame spraying substrate in step (1) is a carbon steel plate, and the spraying raw material is an iron-based alloy powder with the composition of Cr: 17-20, Mo: 6-8, Ni: 3-4, P: 10-13, B: 2.5-3.5, C: 3-3.5, Si: 2-3 (at.%), Fe as the balance, and a particle size of 20-53 μm.

[0016] Furthermore, the particulate material with a micro-nano structure in component A described in step (2) is one or more of nano-silicon dioxide, nano-titanium dioxide, nano-zinc oxide and various MOFs micro-nano particles, and the particle size of the particulate material with a micro-nano structure is 15-30 nm; the photothermal conversion material is one or more of carbon nanotubes, graphene, carbon black material, titanium nitride and black iron oxide, and the particle size of the photothermal conversion material is 10-30 μm; the mass ratio of the particulate material with a micro-nano structure to the photothermal conversion material is: 2 to 4:1.

[0017] Furthermore, the low surface energy organic material providing flexibility in component B described in step (2) is obtained by mixing polydimethylsiloxane, polylactic acid-glycolic acid copolymer (PLGA) or epoxy resin and their respective matching curing agents in a certain mass ratio, wherein the mass ratio of the polydimethylsiloxane to the curing agent is 8 to 12:1.

[0018] Furthermore, the organic binder component C in step (2) is obtained by mixing polyurethane, perfluoropolyether (PFPE) or polyacrylate copolymer and their respective matching curing agents in a certain mass ratio, wherein the mass ratio of the polyurethane to the curing agent is 10:1 to 3.

[0019] Furthermore, the low surface energy organic material in the low surface energy organic material solution providing a super-hydrophobic effect described in step (2) is one or more of perfluorodecyltriethoxysilane, stearic acid, polytetrafluoroethylene and a silane coupling agent, the organic solvent is one or more of ethanol, ethyl acetate and butyl acetate, the mass ratio of the low surface energy organic material to the organic solvent in the low surface energy organic material solution providing a super-hydrophobic effect is 1:95-100, and the amount of the low surface energy organic material solution providing a super-hydrophobic effect added to the organic super-hydrophobic self-heating coating is 200-600 μL / 5g, where 5g is the total mass of the mixture of component A, component B and component C.

[0020] Furthermore, before the coating in step (3), the iron-based amorphous alloy coating having a certain thickness of protrusions on the surface prepared in step (1) is pretreated with acetone solution, deionized water and ethanol in sequence.

[0021] Furthermore, the coating method described in step (3) is coating with a brush or a spray device, and after curing treatment, the coating thickness at the raised parts is 30 to 50 μm, and the coating thickness at the non-raised parts is 150 to 300 μm.

[0022] Furthermore, the curing treatment in step (3) is performed by standing at room temperature for 60 to 72 hours or standing at 80° C. for 4 to 6 hours.

[0023] Furthermore, the contact angle of the iron-based amorphous-organic composite coating is 158.2°, and the surface temperature of the coating rises to 75°C under the intensity of 1 sun. In the ice melting and freezing experiment, the freezing time is long and the melting time is short, achieving super-hydrophobicity, self-heating, and de-icing functions;

[0024] Furthermore, the curing agents in the B component and the C component of step (2) are Desmodur N3300 and Desmodur HT from Covestro, EPIKURE series from BASF, ARADUR series from Huntsman, EPON Curing Agent series from Olin, 593 curing agent, 650 curing agent and T-31 curing agent from Sanmu Group, KC-50 and NT-8075 from Shiquanxing and DC184 and MK1395 from Dow Corning, Fluorolink AD1700 from Solvay, Krytox Silane from Dupont, and Carbosperse from Lubrizol. TM One of the K-700 series; the polylactic acid-glycolic acid copolymer in component B is cured by light.

[0025] The beneficial effects of the present invention are:

[0026] The iron-based amorphous-organic composite coating of the present invention utilizes a mosaic structure constructed by surface texture to enhance the bonding between the metal layer and the organic layer; the super-hydrophobic surface is supplemented by a photothermal effect, combining active deicing with passive deicing, giving the coating anti-icing and deicing functions and long-term protection capabilities. The corrosion resistance of the composite coating prepared by the present invention is better than that of the original iron-based amorphous alloy coating, giving the metal coating surface the functional properties of super-hydrophobicity and self-heating deicing, improving the anti-fouling and anti-icing properties of the metal coating surface while also extending the service life of the anti-icing coating; the staggered mosaic of the organic layer and the metal layer in the composite coating enables the coating surface to maintain effective super-hydrophobic self-heating deicing functions and strong corrosion resistance even after being damaged.

[0027] From a process perspective, the present invention has a simple preparation process, a safe and environmentally friendly preparation process, low cost, a wide range of applicable scenarios, and broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 The figure is a flow chart for preparing the iron-based amorphous-organic composite coating of the present invention;

[0029] Figure 2 The microstructure and morphology of the iron-based amorphous alloy coating prepared in Comparative Example 4 are characterized;

[0030] Among them, (a) is the XRD pattern of the iron-based amorphous alloy coating; (b) is the TEM image of the iron-based amorphous alloy coating; (c) is the SEM image of the cross-section of the iron-based amorphous alloy coating; (d)-(e) are the three-dimensional laser confocal images and cross-sectional profile images of the surface of the iron-based amorphous alloy coating;

[0031] Figure 3 SEM images of the coatings prepared in Comparative Examples 1-3 and Example 1: (a1)-(a3) are Comparative Example 1; (b1)-(b3) are Comparative Example 2; (c1)-(c3) are Comparative Example 3; (d1)-(d3) are Example 1;

[0032] Figure 4 The contact angle statistical histograms of the coatings prepared in Comparative Examples 1-3 and Example 1 and the physical image of the coating surface prepared in Example 1 are shown;

[0033] Figure 5 Curves showing the surface temperature changes over time for the coatings prepared in Comparative Examples 1-3 and Example 1 at 0.5 solar light intensity and 1 solar light intensity;

[0034] Figure 6 Schematic diagram of the process of ice formation experiment and ice melting experiment in Comparative Example 1 and Example 1 respectively;

[0035] Figure 7 This is a comparison of the hydrophobicity of the coatings prepared in Comparative Example 4 and Example 1;

[0036] Figure 8 The self-cleaning effect diagram of the iron-based amorphous-organic composite coating (Example 1) developed by the present invention, wherein (b1) shows the coating morphology before water passes through the surface and with dust on the surface; (b2) shows the coating morphology during water flow; and (b3) shows the coating morphology after water flows through the surface.

[0037] Figure 9 Figure 1 shows the iron-based amorphous-organic composite coating (Example 1) developed in the present invention immersed in HCl solution (pH = 1), NaOH solution (pH = 14), and NaCl solution (pH = 7), where (a) is immersed for 0 hours; (b) is immersed for 24 hours; (c) is immersed for 48 hours; and (d) is immersed for 72 hours.

[0038] Figure 10 This is a hydrophobicity verification diagram of the iron-based amorphous-organic composite coating (Example 1) developed in the present invention after being immersed in HCl solution (pH=1), NaOH solution (pH=14), and NaCl solution (pH=7) for 72 hours;

[0039] Figure 11Figures showing the wear process of the iron-based amorphous-organic composite coating developed in the present invention (Example 1) under loads of 500 g (a1)-(a3), 200 g (b1)-(b3), 100 g (c1)-(c3), and 50 g (d1)-(d3), as well as the hydrophobicity test results after wear;

[0040] Figure 12 The statistical results of the contact angle change of the iron-based amorphous-organic composite coating (Example 1) developed by the present invention after being worn for different cycles under loads of 50g, 100g, 200g, and 500g;

[0041] Figure 13 The SEM image and corresponding EDS results of the surface of the iron-based amorphous-organic composite coating (Example 1) developed by the present invention after wear (500g 80 cycles);

[0042] Figure 14 The potentiodynamic polarization curves of the untreated iron-based amorphous alloy coating (Comparative Example 1) and the iron-based amorphous-organic composite coating before and after wear (Example 1);

[0043] Figure 15 The graph shows the statistical results of the change in surface contact angle of the iron-based amorphous-organic composite coating (Example 1) after different testing methods. DETAILED DESCRIPTION

[0044] The present invention will be further described in detail below in conjunction with the accompanying drawings and Examples. The following examples are intended to facilitate understanding of the present invention and do not have any limiting effect on it. Without departing from the spirit and substance of the present invention, modifications and replacements made to the inventive method, steps or conditions all fall within the scope of the present invention. Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art.

[0045] Example 1

[0046] This embodiment relates to a method for preparing a super-hydrophobic photothermal deicing iron-based amorphous-organic composite coating, specifically by Figure 1 The process shown in the figure is implemented by the following steps:

[0047] S1. Spraying to prepare an iron-based amorphous alloy coating with a certain thickness of protrusions on the surface:

[0048] An iron-based amorphous alloy coating is prepared by supersonic flame spraying on the upper surface of a base carbon steel plate in multiple passes (5 passes in this embodiment): the raw material for spraying is iron-based alloy powder, with a composition of Fe50, Cr18, Mo7.5, Ni3.5, P12, B3, C3.5, Si2.5 (at.%), a particle size of 20-53 μm, and the spraying process parameters are: air pressure: 84 psi; gas pressure: 80 psi; propane flow rate: 140 SLPM; hydrogen flow rate: 25 SLPM; nitrogen flow rate: 20 SLPM; powder feeding rate: 6 rpm; spraying distance: 240 mm. After two passes of spraying, a sieve plate corresponding to the desired convex distribution is placed between the coating and the spray gun (the sieve plate in this embodiment has a plurality of circular through holes evenly distributed on it, made of 316 stainless steel, with a thickness of 0.5 mm, a hole spacing of 1 mm, and a circular hole diameter of 0.5 mm. The sieve plate plays a shielding role, allowing the molten powder to pass through the holes and deposit at a specific position (the substrate surface below the hole) to form convexities, and the rest is deposited on the sieve plate. After the sieve plate is removed, the texture is revealed). An iron-based amorphous alloy coating with convexities of a certain thickness on the surface can be obtained. The thickest part of the convex coating is 400 μm, and the projected area of ​​each convexity is π*0.25 2 mm 2 The area of ​​the protrusions per square meter accounts for 25.68%, and the coating thickness in other places is 200μm (spraying thickness before adding the screen plate).

[0049] S2. Prepare organic super-hydrophobic self-heating coating:

[0050] S2.1 Mix 1.0 g of nano-silicon dioxide powder (particle size 15-30 nm) and 0.5 g of graphene oxide powder (thickness approximately 2 nm, flake diameter 10-15 μm) to obtain component A;

[0051] S2.2 Mix 2.0 g of polydimethylsiloxane and 0.2 g of curing agent (Dow Corning DC184) in a mass ratio of 10:1 to obtain component B.

[0052] S2.3 Mix 1.2 g of polyurethane and 0.3 g of curing agent (Desmodur N3300 from Covestro) in a mass ratio of 4:1 to obtain component C;

[0053] S2.4 Mix 1 g of perfluorodecyltriethoxysilane and 99 g of ethanol and disperse them by ultrasonication for 5 min to obtain a FAS solution (fluoroalkylsilane solution);

[0054] Component A, component B, and component C were fully mixed and added to 40 g of ethyl acetate, ultrasonically dispersed for 5 minutes, and 2 drops (1 drop is calculated as 200 μL, 2 drops are 400 μL in total) of FAS solution were added. After ultrasonic dispersion for 5 minutes, an organic superhydrophobic self-heating coating was obtained.

[0055] S3. The organic super-hydrophobic self-heating coating obtained by S2 is evenly coated on the iron-based amorphous alloy coating obtained by S1, and then allowed to stand until the coating is naturally dry.

[0056] The steps of the coating method are:

[0057] (1) Before coating, the surface of the iron-based amorphous alloy coating was pretreated. The coating was degreased using acetone solution, then cleaned with deionized water, and finally ultrasonically cleaned with ethanol.

[0058] (2) Place the carbon steel plate sprayed with the iron-based amorphous alloy coating flat on the table with the coating facing up, and use a brush, spray bottle or other tools to evenly apply the ultrasonically dispersed organic superhydrophobic self-heating coating (brush until the depressions are basically filled) on the iron-based amorphous alloy coating.

[0059] (3) The organic super-hydrophobic self-heating coating was then allowed to stand for curing, and the coating was allowed to stand at room temperature for 72 hours. The thickness of the organic layer in the concave portion (non-convex portion) after curing was about 200 μm, and the thickness of the organic layer in other portions (convex portion) was about 35 μm.

[0060] Comparative Example 1

[0061] S1. Preparation of iron-based amorphous alloy coating by spraying:

[0062] An iron-based amorphous alloy coating was applied to the upper surface of a carbon steel substrate using two passes of supersonic flame spraying. The raw material used was an iron-based alloy powder with a composition of Fe50, Cr18, Mo7.5, Ni3.5, P12, B3, C3.5, and Si2.5 (at%), with a particle size of 20-53 μm. The spraying parameters were: air pressure: 84 psi; fuel gas pressure: 80 psi; propane flow rate: 140 SLPM; hydrogen flow rate: 25 SLPM; nitrogen flow rate: 20 SLPM; powder feed rate: 6 rpm; and spray distance: 240 mm. The coating thickness was 200 μm.

[0063] Comparative Example 2

[0064] S1. Preparation of iron-based amorphous alloy coating by spraying:

[0065] The preparation process is the same as S1 in Comparative Example 1;

[0066] S2. Prepare organic super hydrophobic coating:

[0067] S2.1 Take 1.0g of nano-silicon dioxide powder (particle size 15-30nm) to obtain component A;

[0068] S2.2 Mix 2.0 g of polydimethylsiloxane and 0.2 g of curing agent (Dow Corning DC184) in a mass ratio of 10:1 to obtain component B.

[0069] S2.3 Mix 1.2 g of polyurethane and 0.3 g of curing agent (Desmodur N3300 from Covestro) in a mass ratio of 4:1 to obtain component C;

[0070] S2.4 Mix 1 g of perfluorodecyltriethoxysilane and 99 g of ethanol and disperse them ultrasonically for 5 min to obtain a FAS solution;

[0071] Component A, component B, and component C were fully mixed and added to 40 g of ethyl acetate, ultrasonically dispersed for 5 minutes, and 2 drops (400 μL) of FAS solution were added, and ultrasonically dispersed for 5 minutes to obtain an organic superhydrophobic coating.

[0072] S3. The organic super-hydrophobic coating obtained by S2 is evenly coated on the iron-based amorphous alloy coating obtained by S1, and then allowed to stand until the coating is naturally dry.

[0073] The steps of the coating method are the same as those in Example 1, and the thickness of the organic layer after curing is about 200 μm.

[0074] Comparative Example 3

[0075] S1. Preparation of iron-based amorphous alloy coating by spraying:

[0076] The preparation process is the same as S1 in Comparative Example 1;

[0077] S2. Prepare organic super-hydrophobic self-heating coating:

[0078] S2.1 Mix 1.0 g of nano-silicon dioxide powder (particle size 15-30 nm) and 0.5 g of graphene oxide powder (thickness approximately 2 nm, flake diameter 10-15 μm) to obtain component A;

[0079] S2.2 Mix 2.0 g of polydimethylsiloxane and 0.2 g of curing agent (Dow Corning DC184) in a mass ratio of 10:1 to obtain component B.

[0080] S2.3 Mix 1.2 g of polyurethane and 0.3 g of curing agent (Desmodur N3300 from Covestro) in a mass ratio of 4:1 to obtain component C;

[0081] S2.4 Mix 1 g of perfluorodecyltriethoxysilane and 99 g of ethanol and disperse them ultrasonically for 5 min to obtain a FAS solution;

[0082] Component A, component B, and component C were fully mixed and added to 40 g of ethyl acetate, ultrasonically dispersed for 5 minutes, and 2 drops (400 μL) of FAS solution were added. After ultrasonic dispersion for 5 minutes, an organic super-hydrophobic self-heating coating was obtained.

[0083] S3. The organic super-hydrophobic self-heating coating obtained by S2 is evenly coated on the iron-based amorphous alloy coating obtained by S1, and then allowed to stand until the coating is naturally dry.

[0084] The steps of the coating method are the same as those in Example 1, and the thickness of the organic layer after curing is about 200 μm.

[0085] Comparative Example 4

[0086] S1. Spraying to prepare an iron-based amorphous alloy coating with a certain thickness of protrusions on the surface:

[0087] The iron-based amorphous alloy coating was prepared by multiple spraying passes on the upper surface of the carbon steel plate using supersonic flame spraying. The specific steps and the thickness of the prepared iron-based amorphous alloy coating were the same as those in Example S1.

[0088] Results analysis: First, the surface morphology of the iron-based amorphous alloy coating prepared in Comparative Example 4 was observed using a scanning electron microscope (SEM). Figure 2 As shown in Figure 2, XRD and TEM results reveal distinct amorphous characteristics. Cross-sectional SEM images, coating profiles, and 3D laser confocal microscopy images reveal a uniformly distributed coating surface texture, forming a regular, alternating pattern of peaks and valleys. This surface morphology effectively expands the coating's surface area, facilitating subsequent operations.

[0089] The SEM images of the coatings prepared in Comparative Examples 1-3 and Example 1 are shown in FIG. Figure 3 As shown, it can be concluded that the preparation quality of the iron-based amorphous alloy coating is good, the organic coating is evenly coated, the coating quality is good, and the addition of photothermal materials helps to refine the surface wrinkles and facilitates the establishment of micro-nano structures.

[0090] Figure 4 The contact angles of a single water droplet on the four coatings above are shown. It can be seen that the coatings prepared in Comparative Example 3 and Experimental Example 1 exhibit good hydrophobicity, with similar contact angles. The iron-based amorphous-organic composite coating with a surface array (Experimental Example 1) has the highest contact angle, at 158.2°. A larger contact angle indicates a smaller solid-liquid contact area, making it more difficult for ice to adhere to the coating surface.

[0091] Figure 5The surface temperature of the above four coatings changes over time under 0.5 sunlight intensity (simulating cloudy day illumination) and 1 sunlight intensity (simulating sunny day illumination). It can be seen that the iron-based amorphous-organic composite coating (Experimental Example 1) developed by the present invention shows the largest temperature rise under both lighting conditions, with the surface temperature reaching a maximum of 52°C under 0.5 sunlight intensity and a maximum of 75°C under 1 sunlight intensity. At the same time, the coating also shows the fastest temperature rise rate in the first 60 seconds, which indicates that the coating has excellent light-to-heat conversion efficiency.

[0092] Figure 6 The following are actual pictures of the freezing and ice-melting experiments conducted on Comparative Example 1 and Experimental Example 1, respectively. In the freezing experiment, after 170 seconds at -15°C without light, 20 μL of liquid water on the surface of Comparative Example 1 was completely frozen, while Example 1 required 385 seconds to completely freeze. In the ice-melting experiment, it took Comparative Example 1 450 seconds at -15°C under the intensity of one sun to completely melt the same amount of ice as in the freezing experiment. At 450 seconds, the temperature of the melted liquid water was 2.3°C and the coating temperature was 15.2°C. Experimental Example 1 only needed 210 seconds to melt the same amount of ice, and at this time the liquid water temperature reached 5.9°C and the coating temperature reached 18.9°C. The experimental example reached a higher temperature in less time, demonstrating faster photothermal deicing efficiency. The above experimental results show that the iron-based amorphous-organic composite coating developed by the present invention has efficient active and passive anti-icing and deicing functions and is an excellent anti-icing coating material.

[0093] Figure 7 By comparing the hydrophobicity experimental results of Comparative Example 4 and Example 1, it is concluded that the hydrophobicity of the coating is derived from the organic super-hydrophobic self-heating coating rather than the surface array. Figure 8-10 It shows that the iron-based amorphous-organic composite coating developed by the present invention not only has good hydrophobicity and exhibits strong self-cleaning ability, but also exhibits excellent corrosion resistance in various environments (acid, alkali, and salt).

[0094] Figure 11 The actual pictures show the iron-based amorphous-organic composite coating developed by the present invention after being worn under loads of 50g, 100g, 200g, and 500g. Figure 12 The statistical results of the change in contact angle of the coating surface after different cycles of wear under different loads are presented. The results show that the coating can still maintain a large contact angle (greater than 150°) after wear and still has good superhydrophobicity. Figure 13The SEM image and corresponding EDS results of the surface of the iron-based amorphous-organic composite coating developed by the present invention after wear (after 80 cycles of 500g wear) show that the iron-based amorphous texture can provide solid mechanical support and effectively prevent the peeling of the organic coating in the depressions during wear. There is still a photothermal superhydrophobic surface with an area fraction of about 81.6% on the surface after wear. After measurement, the contact angle of the surface after wear is greater than 150°, and the residual organic photothermal superhydrophobic coating can still provide effective de-icing and anti-icing functions. Figure 14 Comparison of the potentiodynamic polarization curves of the coating of Example 1 before and after wear with that of Comparative Example 1. Figure 15 The results show that the coating still has much better corrosion resistance than the untreated coating (ie, comparative example 1) after wear.

[0095] To summarize, to ensure anti-icing and de-icing functions, the first requirement is to ensure a contact angle greater than 150°, creating a super-hydrophobic surface and reducing the solid-liquid contact area, which provides passive anti-icing. Secondly, a certain area fraction of photothermal material must be present on the surface to absorb light under a certain illumination intensity and convert it into heat, generating heat, which provides active anti-icing. These results demonstrate that the iron-based amorphous-organic composite coating developed by this invention is a coating material that combines anti-icing and de-icing functions with long-term protection.

Claims

1. A method for preparing a super-hydrophobic photothermal deicing iron-based amorphous-organic composite coating, characterized by: The method comprises the following steps: (1) A multi-pass spraying method is used to prepare an iron-based amorphous alloy coating with a certain thickness of protrusions on the surface. The first 1-5 passes are directly sprayed on the upper surface of the substrate, and the spraying thickness is 30-200 μm. In the subsequent 3-5 passes, a screen plate is added between the coating and the spray gun to obtain an iron-based amorphous alloy coating with a certain thickness of protrusions on the surface; the protrusions are evenly distributed, and the coating thickness at the protrusions is increased by 150-300 μm compared with the spraying thickness before the screen plate is added. The projected area of ​​each protrusion is 0.04-0.5 mm 2 , the area of ​​the protrusions per square meter accounts for 25% to 60%; the sieve plate is a thin plate with holes that are consistent with the profile and distribution of the protrusions; (2) Prepare organic super-hydrophobic self-heating coating: A mixture of three components is prepared: Component A: a mixture of a micro-nanostructured particle material and a photothermal conversion material; Component B: a low-surface-energy organic material that provides flexibility; and Component C: an organic binder. Prepare a low surface energy organic material solution that provides super hydrophobic effect: take the low surface energy organic material in an organic solvent and evenly disperse it; The above-mentioned component A, component B and component C are mixed and added to an organic solvent and uniformly dispersed, and an appropriate amount of a low surface energy organic material solution providing a super-hydrophobic effect is dropped, and an organic super-hydrophobic self-heating coating is obtained after uniform dispersion, wherein the mass ratio of component A, component B, component C to the organic solvent in the organic super-hydrophobic self-heating coating is 1-2:2-3:1-2:30-50; (3) The organic super-hydrophobic self-heating coating obtained in step (2) is evenly coated on the iron-based amorphous alloy coating with a certain thickness of protrusions on the surface prepared in step (1), and cured.

2. The preparation method according to claim 1, wherein: The supersonic flame spraying substrate in step (1) is a carbon steel plate, and the spraying raw material is an iron-based alloy powder with the following components: Cr: 17-20, Mo: 6-8, Ni: 3-4, P: 10-13, B: 2.5-3.5, C: 3-3.5, Si: 2-3 (at.%), Fe as the balance, and a particle size of 20-53 μm.

3. The preparation method according to claim 1, wherein: The micro-nanostructured granular material in component A described in step (2) is one or more of nano-silicon dioxide, nano-titanium dioxide, nano-zinc oxide and various MOFs micro-nano particles, and the particle size of the micro-nanostructured granular material is 15-30 nm; the photothermal conversion material is one or more of carbon nanotubes, graphene, carbon black material, titanium nitride and black iron oxide, and the particle size of the photothermal conversion material is 10-30 μm; the mass ratio of the micro-nanostructured granular material to the photothermal conversion material is: 2 to 4:

1.

4. The preparation method according to claim 1, wherein: The low surface energy organic material providing flexibility in component B described in step (2) is polydimethylsiloxane, polylactic acid-glycolic acid copolymer (PLGA) or epoxy resin and its respective matching curing agent mixed in a certain mass ratio, wherein the mass ratio of the polydimethylsiloxane to the curing agent is 8 to 12:

1.

5. The preparation method according to claim 1, wherein: The organic binder component C described in step (2) is obtained by mixing polyurethane, perfluoropolyether (PFPE) or polyacrylate copolymer and its respective matching curing agent in a certain mass ratio, wherein the mass ratio of the polyurethane to the curing agent is 10:1-3.

6. The preparation method according to claim 1, wherein: The low surface energy organic material in the low surface energy organic material solution providing a super hydrophobic effect described in step (2) is one or more of perfluorodecyltriethoxysilane, stearic acid, polytetrafluoroethylene and a silane coupling agent, the organic solvent is one or more of ethanol, ethyl acetate and butyl acetate, the mass ratio of the low surface energy organic material to the organic solvent in the low surface energy organic material solution providing a super hydrophobic effect is 1:95-100, and the amount of the low surface energy organic material solution providing a super hydrophobic effect in the organic super hydrophobic self-heating coating is 200-600 μL / 5g, where 5g is the total mass of the mixture of component A, component B and component C.

7. The preparation method according to claim 1, wherein: Before the coating in step (3), the iron-based amorphous alloy coating with a certain thickness of protrusions on the surface prepared in step (1) is pretreated with acetone solution, deionized water and ethanol in sequence.

8. The preparation method according to claim 1, wherein: The coating method described in step (3) is to use a brush or a spray device for coating. After curing, the coating thickness at the raised parts is 30 to 50 μm, and the coating thickness at the non-raised parts is 150 to 300 μm.

9. The preparation method according to claim 1, wherein: The curing treatment in step (3) is to stand at room temperature for 60 to 72 hours or at 80° C. for 4 to 6 hours.

10. The preparation method according to any one of claims 1 to 9, characterized in that: The contact angle of the iron-based amorphous-organic composite coating is 158.2°, and the surface temperature of the coating rises to 75°C under the intensity of 1 sun. In the ice melting and freezing experiment, the freezing time is long and the ice melting time is short, achieving super-hydrophobicity, self-heating and deicing functions; the curing agents in the B component and the C component of step (2) are Desmodur N3300 and Desmodur HT of Covestro, EPIKURE series of BASF, ARADUR series of Huntsman, EPON Curing Agent series of Olin, 593 curing agent, 650 curing agent and T-31 curing agent of Sanmu Group, KC-50 and NT-8075 of Shiquanxing and DC184 and MK1395 of Dow Corning, Fluorolink AD1700 of Solvay, Krytox of Dupont, etc. Silane, Carbosperse from Lubrizol TM One of the K-700 series; the polylactic acid-glycolic acid copolymer in component B is cured by light.

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