Anti-icing and wave-transmitting integrated glass fiber composite material and preparation method thereof
By introducing hydrophobic nanoparticles into the anti-icing resin and using laser processing to form a micro-nano structure, the problem of existing materials being unable to simultaneously achieve wave transmission and anti-icing in low-temperature and high-humidity environments has been solved, realizing a highly efficient integrated anti-icing and wave-transmitting glass fiber composite material.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- NORTHWESTERN POLYTECHNICAL UNIV
- Filing Date
- 2026-03-18
- Publication Date
- 2026-05-12
AI Technical Summary
Existing materials struggle to achieve good anti-icing capabilities while maintaining low dielectric loss, and multi-layer coating or complex interface fabrication processes are costly and cannot meet the requirements for wave transmission and anti-icing in low-temperature and high-humidity environments such as radomes.
Hydrophobic nanoparticles were introduced into the anti-icing resin, and a micro-nano scale hydrophobic structure was formed on the surface of the composite material by laser treatment. Combined with glass fiber cloth, an integrated anti-icing and wave-transparent material was prepared.
Without affecting the wave transmission performance, stable anti-icing performance was achieved, reducing the manufacturing cost and improving the material's anti-icing capability and service reliability in low-temperature environments.
Smart Images
Figure CN122013536A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of functional composite materials technology, specifically relating to an integrated anti-icing and wave-transmitting glass fiber composite material and its preparation method. Background Technology
[0002] In the fields of radar and antennas, the outer surfaces of radomes and antenna covers are often exposed to complex working environments of high humidity and low temperature, making them prone to ice buildup. Ice not only increases structural load and interferes with the transmission and reception of electromagnetic signals, but can also cause localized structural damage and even safety accidents. Therefore, materials with both wave transmission and anti-icing functions are crucial for ensuring the stable and efficient operation of radar equipment. However, existing materials struggle to simultaneously meet the requirements of anti-icing and wave transmission. For example, while active electrothermal de-icing methods are highly efficient, the introduction of conductive media increases wave reflection and reduces the material's wave transmittance. Passive anti-icing coatings often suffer from insufficient mechanical durability, easily deteriorating and failing under the erosion of high-speed airflow, raindrop impact, and the corrosive effects of ice-freezing cycles, failing to meet actual service requirements. Therefore, developing materials with both wave transmission and anti-icing functions is of great significance for improving the adaptability and reliability of radar and antennas in harsh environments.
[0003] Fiberglass fabrics possess advantages such as high strength (tensile strength > 3 GPa), corrosion resistance, and good dielectric transparency, demonstrating excellent application potential in scenarios requiring simultaneous structural load-bearing capacity, wave transmission, and environmental tolerance. Chinese patent application CN115877324A discloses a low-dielectric-loss fiberglass material for fabricating radar housings. This technology focuses on improving radar signal transmission quality and reducing clutter reflection; however, it does not consider the icing behavior of the material in low-temperature, high-humidity environments, nor does it address signal attenuation, interface damage, or service reliability issues caused by ice. Therefore, while this type of structure possesses good wave transmission characteristics, it is insufficient to meet the anti-icing requirements of radar domes in cold environments. Chinese patent application CN118832944A discloses an anti-icing and heat storage film suitable for wind turbine blades and its preparation method. It uses hollow fiberglass cloth as an intermediate support layer, and employs a polyurethane-modified epoxy resin bonding coating and a heat storage protective film design, utilizing phase change heat storage materials to achieve temperature regulation and anti-icing functions on the blade surface. However, the multi-layered composite structure of this thermal storage film significantly affects the electromagnetic wave transmission performance, making it unsuitable for applications such as radar domes or communication antenna radomes where strict wave transmission requirements are necessary. Chinese patent application CN120082082A proposes a superhydrophobic self-healing anti-icing film for wind turbine blade de-icing. It achieves anti-icing functionality by constructing a multi-layered structure of shape memory polymer and modified nano-SiO2 superhydrophobic layer on the surface of glass fiber reinforced resin. However, this technology involves multiple precision processes such as microcapsule synthesis and electroplating deposition, resulting in high manufacturing costs. Furthermore, its long-term service stability still requires further verification.
[0004] Analysis of existing preparation processes reveals the following shortcomings: (1) Existing solutions often focus on optimizing a single function, making it difficult to achieve good anti-icing capabilities while maintaining low dielectric loss; (2) Multilayer coating or complex interface preparation processes are costly and cannot meet the requirements of actual service environments. Summary of the Invention
[0005] To overcome the shortcomings of the prior art, the present invention aims to provide an integrated anti-icing and wave-transmitting glass fiber composite material and its preparation method. By introducing hydrophobic nanoparticles into the anti-icing resin, a micro-nano scale hydrophobic structure is generated on the surface of the composite material through laser processing technology without affecting the wave transmission performance. This enables the integrated anti-icing and wave-transmitting glass fiber composite material to have high wave transmittance while maintaining stable anti-icing performance in low-temperature environments.
[0006] To achieve the above objectives, the present invention adopts the following technical solution: A method for preparing an integrated anti-icing and wave-transparent glass fiber composite material includes the following steps: Anti-icing resin and nanoparticles were added to a solvent and mixed evenly to obtain an anti-icing resin mixture containing functional fillers. The anti-icing resin mixture is uniformly impregnated onto the surface of fiberglass cloth using an impregnation process, followed by curing treatment to obtain the cured composite material. In an air environment, laser treatment is performed on the surface of the cured composite material to generate a micro-nano scale hydrophobic structure on the surface of the cured composite material, thereby obtaining the glass fiber composite material that integrates anti-icing and wave transmission.
[0007] Preferably, the anti-icing resin is polydimethylsiloxane, silicone-modified acrylic resin, or polyurethane.
[0008] Preferably, the nanoparticles are at least one of hydrophobic nano-silica, surface-hydrophobic nano-alumina, surface-hydrophobic titanium dioxide, and surface-hydrophobic carbon nanotubes.
[0009] Preferably, the nanoparticles have a particle size of 10-100 nm.
[0010] Preferably, the solvent is ethanol, ethyl acetate, or N,N-dimethylformamide.
[0011] Preferably, in the anti-icing resin mixture, the concentration of the anti-icing resin is 10.5 wt%-11.5 wt%, and the nanoparticles are 0.9%-1.1% of the mass of the anti-icing resin.
[0012] Preferably, the fiberglass cloth is a single-layer plain weave fiberglass cloth, satin weave fiberglass cloth, or twill weave fiberglass cloth, and the thickness of the fiberglass cloth ranges from 0.05 to 2 mm.
[0013] Preferably, when performing laser treatment on the surface of the cured composite material, the laser used is a carbon dioxide laser, an ultraviolet laser, or a femtosecond laser, wherein the wavelength of the carbon dioxide laser is 10.6 μm, the wavelength of the ultraviolet laser is 248-355 nm, and the wavelength of the femtosecond laser is 300-1100 nm; the diameter of the laser direct writing spot is 5-200 μm, the laser power is 1.5-3.0 W, the scanning rate is set to 188-200 mm / s, the number of scans is 1, and the energy density range is 5-25 J / cm². 2 .
[0014] The present invention also provides an integrated anti-icing and wave-transparent glass fiber composite material, which is prepared by the preparation method of the present invention as described above.
[0015] The present invention also provides the application of the anti-icing and wave-transparent integrated glass fiber composite material as described above, which is used to prepare the skin of a radome or antenna radome.
[0016] The present invention has the following beneficial effects: The preparation method of the integrated anti-icing and wave-transmitting glass fiber composite material according to claim 1 of this invention involves uniformly mixing anti-icing resin and nanoparticles in a solvent to obtain a functionalized resin mixture, then using an impregnation process to uniformly coat the glass fiber cloth with the mixture and cure it. Finally, the surface of the cured composite material is laser-treated in an air environment to form a micro-nano scale hydrophobic structure. This method effectively solves the technical defects of existing technologies, such as the difficulty in simultaneously achieving anti-icing and wave-transmitting functions, complex and costly processes, and poor durability of the anti-icing structure. Furthermore, the glass fiber cloth itself possesses excellent dielectric transparency, ensuring effective transmission of electromagnetic waves and avoiding the problem of reduced wave transmittance caused by the introduction of conductive media in traditional active electrothermal de-icing methods. The combination of anti-icing resin and nanoparticles endows the material with basic anti-icing and hydrophobic properties at the matrix level, eliminating the need for additional anti-icing coatings. This avoids interference with wave transmission performance caused by multiple coatings and solves the problem of easy peeling and failure of traditional passive anti-icing coatings. At the same time, the non-contact laser treatment in the air environment only acts on the surface of the material and does not damage the internal structure and dielectric properties. It can enhance the anti-icing effect through the in-situ formed micro-nano hydrophobic structure and flexibly control the treatment area without modifying the overall material. While reducing process costs and processing difficulty, it achieves the synergistic unity of anti-icing and wave transmission functions, significantly improving the reliability of the material in actual service environments and adapting to the needs of radar and antenna applications. Attached Figure Description
[0017] Figure 1 A flowchart illustrating the preparation process of the glass fiber reinforced composite material with integrated anti-icing and wave-transmitting properties provided by this invention. Figure 2 These are scanning electron microscope images comparing the surface morphology of composite material samples prepared under different process conditions according to the present invention. Figure 3 This is a comparison diagram of the static water contact angles of composite material samples prepared under different process conditions according to the present invention; Figure 4 A comparison of the freezing time of composite material samples prepared under different process conditions of the present invention at -20℃. Figure 5 This is a comparison of the ice bonding strength of composite material samples prepared under different process conditions of the present invention at -20℃. Figure 6 This is a comparison of the average transmittance of composite material samples prepared under different process conditions according to the present invention in the X-band. Detailed Implementation
[0018] To enable those skilled in the art to understand the features and effects of the present invention, the terms and expressions used in the specification and claims are explained and defined in general below. Unless otherwise specified, all technical and scientific terms used herein have the ordinary meaning understood by those skilled in the art regarding the present invention, and in case of conflict, the definitions in this specification shall prevail.
[0019] The theories or mechanisms described and disclosed herein, whether right or wrong, should not in any way limit the scope of the invention, that is, the contents of the invention can be implemented without being limited by any particular theory or mechanism.
[0020] In this document, all features defined by numerical ranges or percentage ranges, such as numerical values, quantities, contents, and concentrations, are for the sake of brevity and convenience only. Accordingly, descriptions of numerical ranges or percentage ranges should be considered as covering and specifically disclosing all possible sub-ranges and individual numerical values (including integers and fractions) within those ranges.
[0021] In this article, unless otherwise specified, “contains,” “includes,” “containing,” “has,” or similar terms cover the meanings of “composed of” and “mainly composed of,” for example, “A contains a” covers the meanings of “A contains a and others” and “A contains only a.”
[0022] For the sake of brevity, not all possible combinations of the technical features in each implementation scheme or embodiment are described herein. Therefore, as long as there is no contradiction in the combination of these technical features, the technical features in each implementation scheme or embodiment can be combined arbitrarily, and all possible combinations should be considered within the scope of this specification.
[0023] like Figure 1 As shown, this invention proposes an integrated anti-icing and wave-transmitting glass fiber composite material and its preparation method, belonging to the field of functional composite materials technology. This method uses an impregnation and curing process to composite anti-icing resin, hydrophobic nanoparticles, and glass fiber fabric; subsequently, laser surface treatment is used to obtain a micron-scale structure, forming a micro-nano composite hydrophobic structure with the exposed nanoparticles, thus improving the anti-icing performance while maintaining high wave transmittance. By controlling the laser treatment area, the hydrophobicity can be regionally regulated. The resulting material can be used in applications requiring high wave transmittance and stable anti-icing capabilities, such as radomes and antenna covers, and specifically, it can be used to manufacture skin materials.
[0024] In one specific embodiment, a method for preparing an integrated anti-icing and wave-transparent glass fiber composite material includes the following steps: 1) Anti-icing resin and nanoparticles as functional fillers are added to an organic solvent. The mixture is stirred and ultrasonically treated to ensure uniform mixing of the anti-icing resin, nanoparticles, and organic solvent, resulting in an anti-icing resin mixture containing the functional filler. The anti-icing resin is polydimethylsiloxane, silicone-modified acrylic resin, or polyurethane. The nanoparticles have a particle size of 10-100 nm and function to form a micro-nano composite structure on the material surface to create a hydrophobic and anti-icing surface. They can be at least one of hydrophobic nano-silica, surface-hydrophobic nano-alumina, surface-hydrophobic titanium dioxide, and surface-hydrophobic carbon nanotubes. The organic solvent can be ethyl acetate, ethanol, or N,N-dimethylformamide. In the anti-icing resin mixture, the concentration of the anti-icing resin is 10.5 wt%-11.5 wt%, and the nanoparticles constitute 0.9%-1.1% of the anti-icing resin mass.
[0025] 2) An impregnation process is used to uniformly impregnate the anti-icing resin mixture onto the surface of the fiberglass cloth. After vacuum degassing, a curing treatment is performed. The impregnation can be carried out under normal pressure or in a vacuum, ensuring that the anti-icing resin mixture is uniformly distributed on the surface of the fiberglass cloth. The fiberglass fabric can be a single-layer plain weave fiberglass fabric, a satin weave fiberglass fabric, or a twill weave fiberglass fabric; the thickness of the fiberglass fabric ranges from 0.05 to 2 mm.
[0026] 3) After curing, the composite material is subjected to laser treatment on a portion of its surface in an air environment to achieve regional control of its hydrophobic function, thus producing a glass fiber reinforced composite material with integrated anti-icing and wave-transmitting functions. The laser used can be a carbon dioxide laser, an ultraviolet laser, or a femtosecond laser. The wavelength of the carbon dioxide laser is 10.6 μm, the wavelength of the ultraviolet laser is 248-355 nm, and the wavelength of the femtosecond laser is 300-1100 nm. The laser spot diameter is 5-200 μm, the laser power is 1.5-3.0 W, the scanning rate is set to 188-200 mm / s, the number of scans is 1, and the energy density range is 5-25 J / cm³. 2 .
[0027] More preferably, when a carbon dioxide laser is used, the wavelength of the laser is 10.6 μm, the diameter of the spot is 50-150 μm, and the energy density is 10-15 J / cm². 2 .
[0028] In the above-mentioned solution of the present invention, laser surface treatment technology, with its high precision, non-contact processing and customizable processing area, promotes breakthroughs in intelligent surface engineering and extreme environment protection, and provides a new research idea for solving the problem of simultaneously optimizing anti-icing / wave transmission performance. It has important basic research value and engineering application potential.
[0029] The glass fiber reinforced composite material prepared by the above-described preparation method of the present invention, which integrates anti-icing and wave transmission, has the following characteristics: According to the test, the wave transmission rate of the composite material of the present invention is ≥90% in the 8.2-12.4GHz frequency band (i.e., X-band), and the ice bonding strength is ≤10kPa at -20℃ and 90% relative humidity. It can meet the requirements of synergistic wave transmission and anti-icing performance for applications such as radomes and antenna covers, and can be used in anti-icing fields such as radomes and antenna covers that require both wave transmission and anti-icing performance.
[0030] The present invention will be further illustrated below with reference to specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the teachings of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by the appended claims.
[0031] The following examples use instruments and equipment conventional in the art. Experimental methods in the following examples, unless otherwise specified, are generally performed under conventional conditions or as recommended by the manufacturer. All raw materials used in the following examples are conventional commercially available products with specifications conventional in the art. In this specification and the following examples, unless otherwise specified, "%" refers to weight percentage, "parts" refers to parts by weight, and "ratio" refers to weight proportion.
[0032] Example 1: The preparation method of the integrated anti-icing and wave-transmitting glass fiber composite material in this embodiment includes the following steps: Weigh 10 g of polydimethylsiloxane prepolymer and 1 g of curing agent, dissolve them in 89 g of ethyl acetate, stir magnetically for 30 minutes, add 1 g of hydrophobic nano silica, and continue ultrasonic dispersion for 20 minutes to obtain a uniform PDMS / SiO2 composite resin solution.
[0033] A single layer of E-type plain weave glass fiber cloth with a thickness of 0.26 mm was cut into 100 mm × 100 mm samples and placed in the above-mentioned resin solution. The samples were then impregnated under vacuum for 20 minutes to ensure that the resin fully wetted the fiber gaps. After removal, the samples were degassed under vacuum for 20 minutes, followed by step curing. The samples were first treated in a 70°C oven for 30 minutes, then heated to 110°C and held for 30 minutes to obtain a glass fiber reinforced substrate with a PDMS / SiO2 composite structure on its surface.
[0034] In an air environment, the sample was placed on a CO2 laser platform with a wavelength of 10.6 μm. An 80 mm × 80 mm area was designed for direct laser scanning. The laser power was 3 W, the scanning rate was set to 189 mm / s, and the number of scans was 1, corresponding to an energy density of 12.5 J / cm². 2 .
[0035] See Figure 2 Figure (a) shows the scanning electron microscope structure of the composite material surface without laser treatment. The surface is relatively smooth with a few undulating structures. See also... Figure 2 Figure (b) shows the surface of the sample after laser treatment, exhibiting regular micron-level undulations and exposed nanoparticle structures under a scanning electron microscope. The surface roughness increased from 0.75 μm before treatment to 1.12 μm. The Shore A hardness of the pure PDMS matrix before and after laser treatment was measured. The results show that the Shore A hardness of PDMS increased from 40 before laser treatment to 48 after laser treatment. The above structures demonstrate that laser treatment can effectively adjust the surface roughness, thereby forming a micro / nano hydrophobic structure and improving hydrophobicity. At the same time, it can also increase the surface hardness, forming a modulus adaptation at the ice-solid interface when ice accumulates on the surface, thereby reducing the ice adhesion strength.
[0036] Under the conditions described in this study, a glass fiber composite material sample with excellent and stable hydrophobic and icing-repellent properties was successfully prepared. See also... Figure 3 The measured water contact angle increased from 105° in the untreated case to 135° in this embodiment; see [link to relevant documentation]. Figure 4 The measured freezing time of water droplets was increased from 255 seconds in the untreated case to 300 seconds in this embodiment; see also Figure 5 The ice bonding strength decreased from 7.8 kPa to 5.5 kPa in this embodiment. See also... Figure 6 The laser treatment did not introduce a highly conductive carbonized layer on the surface, which kept the X-band transmittance of the composite material at 92%, meeting the 90% level required for applications such as radar, and thus it has application value in the fields of wave transmission and de-icing.
[0037] Comparative Example 1: The preparation method of this comparative composite material includes the following steps: Weigh 10 g of polydimethylsiloxane prepolymer and 1 g of curing agent, dissolve them in 89 g of ethyl acetate, stir magnetically for 30 minutes, add 1 g of hydrophobic nano silica, and continue ultrasonic dispersion for 20 minutes to obtain a uniform PDMS / SiO2 composite resin solution.
[0038] A single layer of E-type plain weave glass fiber cloth with a thickness of 0.26 mm was cut into 100 mm × 100 mm samples and placed in the above-mentioned resin solution. The samples were then impregnated under vacuum for 20 minutes to ensure that the resin fully wetted the fiber gaps. After removal, the samples were degassed under vacuum for 20 minutes, followed by step curing. The samples were first treated in a 70°C oven for 30 minutes, then heated to 110°C and held for 30 minutes to obtain a glass fiber reinforced substrate with a PDMS / SiO2 composite structure on its surface.
[0039] In an air environment, the sample was placed on a CO2 laser platform with a wavelength of 10.6 μm. An 80 mm × 80 mm area was designed for direct laser scanning. The laser power was 1.5 W, the scanning rate was set to 189 mm / s, and the number of scans was 1, corresponding to an energy density of 6.25 J / cm³. 2 .
[0040] like Figure 2 As shown in Figure (c), the laser-treated sample surface exhibits a relatively smooth microstructure under a scanning electron microscope. The material surface is relatively smooth with a roughness of 0.76 μm, similar to the original surface without laser treatment. See also Figure 3 The measured water contact angle increased from 105° in the untreated case to 115° in this comparative example; see [link to relevant documentation]. Figure 4 The measured freezing time of water droplets increased from 255 s in the untreated sample to 265 s in this comparative example; see [link to related data]. Figure 5 The ice bonding strength decreased from 7.8 kPa to 7.2 kPa in this comparative example; See also... Figure 6 The laser treatment did not introduce a highly conductive carbonized layer on the surface and had a weaker impact on the surface structure than in Example 1, resulting in the X-band transmittance of the composite material remaining at 93%. These results indicate that when the laser power is low, it is insufficient to construct a hydrophobic structure on the surface of the glass fiber composite material.
[0041] Comparative Example 2: The preparation method of this comparative composite material includes the following steps: Weigh 10 g of polydimethylsiloxane prepolymer and 1 g of curing agent, dissolve them in 89 g of ethyl acetate, stir magnetically for 30 minutes, add 1 g of hydrophobic nano silica, and continue ultrasonic dispersion for 20 minutes to obtain a uniform PDMS / SiO2 composite resin solution.
[0042] A single layer of E-type plain weave glass fiber cloth with a thickness of 0.26 mm was cut into 100 mm × 100 mm samples and placed in the above-mentioned resin solution. The samples were then impregnated under vacuum for 20 minutes to ensure that the resin fully wetted the fiber gaps. After removal, the samples were degassed under vacuum for 20 minutes, followed by step curing. The samples were first treated in a 70°C oven for 30 minutes, then heated to 110°C and held for 30 minutes to obtain a glass fiber reinforced substrate with a PDMS / SiO2 composite structure on its surface.
[0043] In an air environment, the sample was placed on a CO2 laser platform with a wavelength of 10.6 μm. An 80 mm × 80 mm area was designed for direct laser scanning. The laser power was 3 W, the scanning rate was set to 189 mm / s, and the number of scans was 1, corresponding to an energy density of 25 J / cm². 2 See also Figure 3 The measured water contact angle increased from 105° in the untreated sample to 137° in this comparative example; see [link to related documentation]. Figure 4 The measured freezing time of water droplets increased from 255 s in the untreated sample to 305 s in this comparative example; see [link to relevant documentation]. Figure 5 The ice bonding strength decreased from 7.8 kPa to 5.4 kPa in the comparative example, exhibiting higher hydrophobic and ice-repellent properties. However, under this laser process, a partial carbonization layer appeared on the material surface, increasing conductivity and resulting in a significant decrease in transmittance to 82%. Figure 6 As shown, this results in the failure to meet the integrated requirements for anti-icing and wave transmission of radar materials.
[0044] Comparative Example 3: The preparation method of this comparative composite material includes the following steps: Weigh 10 g of polydimethylsiloxane prepolymer and 1 g of curing agent, dissolve them in 89 g of ethyl acetate, stir magnetically for 30 minutes, add 5 g of hydrophobic nano silica, and continue ultrasonic dispersion for 20 minutes to obtain a uniform PDMS / SiO2 composite resin solution.
[0045] A single layer of E-type plain weave glass fiber cloth with a thickness of 0.26 mm was cut into 100 mm × 100 mm samples and placed in the above-mentioned resin solution. The samples were then impregnated under vacuum for 20 minutes to ensure that the resin fully wetted the fiber gaps. After removal, the samples were degassed under vacuum for 20 minutes, followed by step curing: first, the samples were treated in a 70°C oven for 30 minutes, then heated to 110°C and held for 30 minutes to obtain a glass fiber reinforced substrate with a PDMS / SiO2 composite structure on its surface.
[0046] In an air environment, the sample was placed on a CO2 laser platform with a wavelength of 10.6 μm. An 80 mm × 80 mm area was designed for direct laser scanning. The laser power was 3 W, the scanning rate was set to 189 mm / s, and the number of scans was 1, corresponding to an energy density of 12.5 J / cm². 2 .
[0047] When the content of nano-hydrophobic silica particles is excessive, the hydrophobicity of the composite material is significantly improved after laser treatment. (See [reference needed]) Figure 3 The water contact angle of the composite material obtained in this comparative example increased to 142°; see [link to related documentation]. Figure 4 The measured freezing time of water droplets increased from 255 s in the untreated sample to 310 s in this comparative example; see [link to related data]. Figure 5 The ice-bonding strength decreased from 7.8 kPa to 5.1 kPa in the comparative example, exhibiting high hydrophobic and ice-repellent properties. However, excessive exposure of nano-hydrophobic silica particles on the surface led to their detachment during subsequent characterization, reducing stability. Multiple experimental measurements revealed a gradually decreasing contact angle. Simultaneously, excessive discontinuous phases in the matrix also resulted in reduced transmittance; the measured transmittance in the X-band was 78%. (See [reference needed]). Figure 6 The above results indicate that an excessive amount of nano-hydrophobic filler can affect the structural stability of glass fiber composites and also impair their wave transmission performance; therefore, their content needs to be controlled within a reasonable range.
[0048] Comparative Example 4: The preparation method of this comparative composite material includes the following steps: Weigh 10 g of polydimethylsiloxane prepolymer and 1 g of curing agent, dissolve them in 89 g of ethyl acetate, stir magnetically for 30 minutes, add 1 g of hydrophobic nano silica, and continue ultrasonic dispersion for 20 minutes to obtain a uniform PDMS / SiO2 composite resin solution.
[0049] A single layer of E-type plain weave glass fiber cloth with a thickness of 0.26 mm was cut into 100 mm × 100 mm samples and placed in the above-mentioned resin solution. The samples were then impregnated under vacuum for 20 minutes to ensure that the resin fully wetted the fiber gaps. After removal, the samples were degassed under vacuum for 20 minutes, followed by step curing: first, the samples were treated in a 70°C oven for 30 minutes, then heated to 110°C and held for 30 minutes to obtain a glass fiber reinforced substrate with a PDMS / SiO2 composite structure on its surface.
[0050] In an air environment, the sample was placed on a CO2 laser platform with a wavelength of 10.6 μm. An 80 mm × 80 mm area was designed for direct laser scanning. The laser power was 6 W, the scanning rate was set to 189 mm / s, and the number of scans was 1, corresponding to an energy density of 50 J / cm³. 2 .
[0051] like Figure 2 As shown in Figure (d), the laser-treated sample surface exhibits a distinct carbonized layer and structural collapse under a scanning electron microscope, with localized burn-through areas. Surface roughness cannot be accurately characterized due to the uneven accumulation of the carbonized layer. See also... Figure 3 The measured water contact angle decreased to 30°, indicating hydrophilicity; see [link / reference]. Figure 4 The freezing time of water droplets was measured to decrease from 255 s in the untreated sample to 180 s in this comparative example; see [link to relevant documentation]. Figure 5 The ice-bonding strength increased from 7.8 kPa to 9.6 kPa in the comparative example, exhibiting extremely low hydrophobicity and ice-repellency. A distinct carbonization layer appeared on the material surface, resulting in a significant decrease in wave transmittance to 67%. Figure 6 As shown, this results in the material failing to meet the requirements of radar materials for integrated anti-icing and wave transmission.
[0052] Figure 3 The water contact angle of the composite material under six different processes, namely, the untreated composite material, Example 1, Comparative Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 4. For Example 1, the contact angle increased from 105° to 135°, significantly enhancing hydrophobicity. For Comparative Example 1, the contact angle was 110°, indicating that the laser parameters were insufficient to form micro / nano hydrophobic structures on the surface, limiting the improvement in hydrophobicity. For Comparative Example 2, the contact angle was 137°, significantly improving hydrophobicity. For Comparative Example 3, the water contact angle increased to 142°, indicating that nano-silica particles could alter the surface wetting state and improve hydrophobicity. However, due to the tendency for excessive silica to detach, the contact angle gradually decreased with increasing test counts. For Comparative Example 4, the contact angle decreased from 105° to 30°. The material surface exhibited severe degradation in hydrophobicity due to the irregular morphology and chemical composition changes of the carbonized layer, resulting in a significant decrease in contact angle and obvious wetting inhomogeneity. This indicated that excessive laser power caused carbonization on the material surface, which was detrimental to improving the hydrophobic and anti-icing properties of the composite material.
[0053] Figure 4The time required for 100 μL of deionized water to completely freeze in an environment with a surface temperature of -20°C was measured for six different processes: untreated composite material, Example 1, Comparative Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 4. For Example 1, the time required for complete freezing of the deionized water droplet increased from 255 s to 300 s, indicating that laser treatment with appropriate power can improve the anti-icing performance of the composite material. For Comparative Example 1, the time required for complete freezing of the deionized water droplet was 265 s, indicating a weaker anti-icing effect than Example 1. For Comparative Example 2, the time required for complete freezing of the deionized water droplet was 305 s. For Comparative Example 3, the time required for complete freezing of the deionized water droplet was 310 s, but due to the easy shedding of excessive silica, the freezing time gradually increased with the number of tests. For Comparative Example 4, the time required for complete freezing of the deionized water droplet was only 180 s, indicating that excessive laser power deteriorated the anti-icing performance of the composite material.
[0054] Figure 5 The ice-bonding strength of the composite material under six different processes (untreated, Example 1, Comparative Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 4) at a surface temperature of -20°C was measured. For Example 1, the ice-bonding strength decreased from 7.8 kPa to 5.5 kPa, indicating that appropriate laser power treatment can improve the anti-icing performance of the composite material. For Comparative Example 1, the ice-bonding strength was 7.2 kPa, indicating a weaker anti-icing effect than Example 1. For Comparative Example 2, the ice-bonding strength was 5.4 kPa. For Comparative Example 3, the ice-bonding strength was 5.1 kPa, but due to the easy shedding of excessive silica, the ice-bonding strength gradually increased with the number of tests. For Comparative Example 4, the ice-bonding strength increased to 9.6 kPa, indicating that excessive laser power deteriorated the anti-icing performance of the composite material.
[0055] Figure 6 The transmittance of the composite materials in the X-ray band was measured under six different processes: untreated composite material, Example 1, Comparative Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 4. The untreated sample had an average transmittance of 94%; Comparative Example 1 and Example 1 were next, with average transmittances of 93% and 92%, respectively; Comparative Example 2 and Comparative Example 3 were even lower, with average transmittances of 82% and 78%, respectively; and Comparative Example 4 had the lowest average transmittance of only 67%. The experiment shows that when the content of hydrophobic nano-silica and the energy density are controlled within the critical threshold, the average transmittance can still be higher than 90%, meeting the requirements of actual service. However, when the silica content is too high, leading to discontinuity in the matrix phase, or when the power is too high, resulting in significant carbonization, the reflection of waves is enhanced, leading to a significant decrease in transmittance.
[0056] The experimental results show that this invention, by using glass fiber fabric as reinforcement, low surface energy polymer as anti-icing resin, and hydrophobic nanoparticles as functional fillers, achieves a transmittance of over 90% in the X-band while simultaneously generating a micron-scale structure on the surface of the composite material through laser modification. This structure, together with the nanoparticles in the matrix, forms a micro-nano composite hydrophobic structure, transforming the wetted state of water droplets into a Cassie-Baxter state, thus improving the hydrophobic and anti-icing properties of the composite material. Furthermore, laser treatment increases the local hardness of the composite material surface, promoting stress concentration at the ice / solid interface through local modulus differences, making the ice layer easier to detach under external disturbances. These factors allow laser treatment to significantly improve surface hydrophobicity without affecting transmittance, achieving highly efficient anti-icing. Its static water contact angle can reach over 140°, with a contact angle hysteresis reduced to around 5°, effectively suppressing the retention and spreading of supercooled water droplets and significantly delaying ice formation. This technology achieves a synergistic design of wave transmission and anti-icing without the need for conductive layers or additional coatings. Furthermore, the non-contact laser processing avoids damage to the substrate. By controlling the treated area, the hydrophobic and anti-icing properties of areas prone to icing can be improved without requiring laser modification of the entire composite material, effectively reducing process costs.
[0057] This invention uses the above-mentioned method to prepare a micro-nano hydrophobic structure by using PDMS as the anti-icing resin matrix and hydrophobic nano-silica particles as functional fillers, and by laser surface modification to obtain a micro-nano hydrophobic structure. The prepared anti-icing and wave-transmitting glass fiber composite material has a wave transmittance of not less than 90% in the 8.2-12.4GHz frequency band and an ice bonding strength of less than 10kPa in a high humidity environment of -20℃, thus possessing both excellent passive anti-icing performance and high wave transmittance characteristics.
[0058] The above content is only for illustrating the technical concept of the present invention and should not be construed as limiting the scope of protection of the present invention. Any modifications made to the technical solution based on the technical concept proposed in this invention shall fall within the scope of protection of the claims of this invention.
Claims
1. A method for preparing an integrated anti-icing and wave-transparent glass fiber composite material, characterized in that, Includes the following processes: Anti-icing resin and nanoparticles were added to a solvent and mixed evenly to obtain an anti-icing resin mixture containing functional fillers. The anti-icing resin mixture is uniformly impregnated onto the surface of fiberglass cloth using an impregnation process, followed by curing treatment to obtain the cured composite material. In an air environment, laser treatment is performed on the surface of the cured composite material to generate a micro-nano scale hydrophobic structure on the surface of the cured composite material, thereby obtaining the glass fiber composite material that integrates anti-icing and wave transmission.
2. The method for preparing an integrated anti-icing and wave-transparent glass fiber composite material according to claim 1, characterized in that, The anti-icing resin is made of polydimethylsiloxane, silicone-modified acrylic resin, or polyurethane.
3. The method for preparing an integrated anti-icing and wave-transparent glass fiber composite material according to claim 1, characterized in that, The nanoparticles are at least one of hydrophobic nano-silica, surface-hydrophobic nano-alumina, surface-hydrophobic titanium dioxide, and surface-hydrophobic carbon nanotubes.
4. The method for preparing an integrated anti-icing and wave-transmitting glass fiber composite material according to claim 1, characterized in that, The nanoparticles have a particle size of 10-100 nm.
5. The method for preparing an integrated anti-icing and wave-transmitting glass fiber composite material according to claim 1, characterized in that, The solvent used is ethanol, ethyl acetate, or N,N-dimethylformamide.
6. A method for preparing an integrated anti-icing and wave-transparent glass fiber composite material according to any one of claims 1-5, characterized in that, In the anti-icing resin mixture, the concentration of anti-icing resin is 10.5 wt%-11.5 wt%, and the nanoparticles are 0.9%-1.1% of the mass of anti-icing resin.
7. The method for preparing an integrated anti-icing and wave-transparent glass fiber composite material according to claim 1, characterized in that, The fiberglass cloth is a single-layer plain weave fiberglass cloth, satin weave fiberglass cloth, or twill weave fiberglass cloth, and the thickness of the fiberglass cloth ranges from 0.05 to 2 mm.
8. A method for preparing an integrated anti-icing and wave-transmitting glass fiber composite material according to claim 1 or 7, characterized in that, When performing laser treatment on the surface of the cured composite material, the laser used is a carbon dioxide laser, an ultraviolet laser, or a femtosecond laser. The wavelength of the carbon dioxide laser is 10.6 μm, the wavelength of the ultraviolet laser is 248-355 nm, and the wavelength of the femtosecond laser is 300-1100 nm. The laser direct writing spot diameter is 5-200 μm, the laser power is 1.5-3.0 W, the scanning rate is set to 188-200 mm / s, the number of scans is 1, and the energy density range is 5-25 J / cm². 2 .
9. A glass fiber composite material that integrates anti-icing and wave transmission, characterized in that, The integrated anti-icing and wave-transmitting glass fiber composite material is prepared by any one of the preparation methods of claims 1-8.
10. The application of the integrated anti-icing and wave-transmitting glass fiber composite material according to claim 9, characterized in that, The integrated anti-icing and wave-transparent glass fiber composite material is used to prepare the skin of radar domes or antenna radomes.