Ablation-resistant resin-based fiber-reinforced composite material based on heat confinement effect and preparation method thereof

Abstract

This invention relates to the field of ablation-resistant materials technology, and in particular to an ablation-resistant resin-based fiber-reinforced composite material based on the heat confinement effect and its preparation method. The ablation-resistant resin-based fiber-reinforced composite material includes an ablation-resistant layer; the ablation-resistant layer comprises alternating stacked first and second ablation-resistant sublayers; both the first and second ablation-resistant sublayers include a prepreg layer and an outer layer disposed on at least one surface of the prepreg layer; the prepreg layer is a modified fiber cloth prepreg, and the modified fiber cloth is a fiber cloth filled with a first filler; the outer layer contains a second filler; the first and second fillers in the first and second ablation-resistant sublayers are each independently selected from either a thermally conductive filler or a thermally insulating filler. This invention utilizes the principle of multidimensional heat induction to construct thermal pathways and thermal gradients within the material, achieving a heat confinement effect and synergistically enhancing the mechanical properties and ablation resistance of the composite material.

Description

Technical Field

[0001] This invention relates to the field of ablation-resistant materials technology, and in particular to an ablation-resistant resin-based fiber-reinforced composite material based on the heat confinement effect and its preparation method. Background Technology

[0002] Ablation-resistant materials are a class of materials that achieve thermal protection through physical and chemical changes such as decomposition, melting, evaporation, sublimation, and erosion under the influence of heat flow. They are indispensable key engineering materials in the field of advanced aerospace equipment. As the speed of spacecraft continues to advance towards hypersonic speeds, their application scenarios have gradually expanded to near-Earth orbit and even deep space. The service thermal environment is becoming increasingly harsh, the aerodynamic heating time is significantly extended, and the instantaneous temperature of critical parts can exceed 2000℃, which places higher demands on the ablation resistance of materials.

[0003] Resin-based fiber-reinforced composites are widely considered ideal ablation-resistant materials due to their ability to maintain structural stability for extended periods at 800°C. However, the inherent chemical reactivity of the resin matrix makes these composites unsuitable for use in more demanding thermal environments. Currently, research to improve the ablation resistance of these composites focuses on two main directions: first, modifying the resin matrix to enhance its char-forming ability and flame-retardant properties; and second, introducing low-thermal-conductivity fillers into the resin matrix to reduce the material's thermal conductivity, thereby improving its ablation resistance. However, these strategies often result in a significant decrease in the material's mechanical properties. More importantly, they lack the ability to systematically induce and regulate internal heat, hindering further improvements in the material's ablation resistance.

[0004] In view of this, the present invention is hereby proposed. Summary of the Invention

[0005] The purpose of this invention is to provide an ablation-resistant resin-based fiber-reinforced composite material based on the heat confinement effect and its preparation method. This invention utilizes the principle of multidimensional heat induction to construct thermal pathways and thermal gradients within the material, thereby achieving the heat confinement effect and synergistically enhancing the mechanical properties and ablation resistance of the composite material.

[0006] To achieve the above-mentioned objectives of the present invention, the present invention adopts the following technical solution: In a first aspect, the present invention provides an ablation-resistant resin-based fiber-reinforced composite material based on the heat confinement effect, comprising an ablation-resistant layer; the ablation-resistant layer comprises an alternately stacked first ablation-resistant sublayer and ablation-resistant sublayer; Both the first ablation-resistant sublayer and the second ablation-resistant sublayer include a prepreg layer and an outer layer disposed on at least one side surface of the prepreg layer; The prepreg layer is a prepreg of modified fiber cloth, and the modified fiber cloth is a fiber cloth filled with a first filler; the outer layer contains a second filler. The first filler and the second filler in the first ablation-resistant sublayer and the second ablation-resistant sublayer are each independently selected from either thermally conductive filler or thermally insulating filler.

[0007] Furthermore, the total number of stacked layers of the first ablation-resistant sublayer and the second ablation-resistant sublayer is 14 to 70.

[0008] Furthermore, the first filler and the second filler in the first ablation-resistant sublayer are each independently selected from either thermally conductive filler or thermally insulating filler; the first filler and the second filler in the second ablation-resistant sublayer are each independently selected from either thermally conductive filler or thermally insulating filler.

[0009] Furthermore, in the first ablation-resistant sublayer or the second ablation-resistant sublayer, the total mass of the first filler and the second filler is 20% to 40% of the fiber cloth.

[0010] Furthermore, in the first ablation-resistant sublayer or the second ablation-resistant sublayer, the mass of the first filler is 10% to 20% of the mass of the fiber cloth.

[0011] Furthermore, in the first ablation-resistant sublayer or the second ablation-resistant sublayer, the mass of the second filler is 10% to 20% of the mass of the fiber cloth.

[0012] Furthermore, the thermal insulation filler includes silicon dioxide, and the thermally conductive filler includes at least one of boron nitride, silicon carbide, and boron carbide.

[0013] Furthermore, the first filler and the second filler are each independently selected from either a surface-modified thermally conductive filler or a thermally insulating filler.

[0014] Furthermore, in the prepreg layer, the mass ratio of the fiber cloth to the resin is (6.5~7.5):(3.5~2.5).

[0015] Furthermore, the thickness of the prepreg layer is 0.20~0.22mm.

[0016] Furthermore, the resin used in the prepreg layer is a thermosetting resin. Further, the thermosetting resin includes at least one of epoxy resin and phenolic resin.

[0017] Furthermore, the fiber cloth includes at least one of basalt fiber cloth, carbon fiber cloth, and glass fiber cloth.

[0018] Furthermore, the ablation-resistant resin-based fiber-reinforced composite material also includes a load-bearing inner layer; the ablation-resistant layer is disposed on both sides of the load-bearing inner layer.

[0019] Furthermore, the inner bearing layer includes at least one inner bearing layer sublayer.

[0020] Furthermore, the number of the supporting inner sublayer accounts for 14% to 85% of the total number of the first ablation-resistant sublayer, the second ablation-resistant sublayer, and the supporting inner sublayer.

[0021] Furthermore, the supporting inner sublayer comprises a prepreg of unmodified fiber cloth.

[0022] Furthermore, adjacent load-bearing inner sublayers are stacked to form the load-bearing inner layer, and the ablation-resistant layers are respectively disposed on two opposite outer sides of the load-bearing inner layer. Furthermore, the ablation-resistant layers are symmetrically disposed on two opposite outer sides of the load-bearing inner layer.

[0023] Furthermore, the ablation-resistant layer and / or the load-bearing inner layer are bonded together by hot pressing.

[0024] In a second aspect, the present invention provides a method for preparing an ablation-resistant resin-based fiber-reinforced composite material based on the heat confinement effect provided in the first aspect, comprising the following steps: (a) The dispersion containing the first filler is introduced into the fiber cloth using vacuum, and then dried to obtain the modified fiber cloth; (b) The resin is coated onto the modified fiber cloth by a coating method to obtain a prepreg of the modified fiber cloth; (c) Spray a dispersion containing a second filler onto the surface of the prepreg of the modified fiber cloth, and dry it to form an outer layer to obtain an ablation-resistant sublayer; (d) The ablation-resistant sublayers are stacked alternately and hot-pressed.

[0025] This invention provides another method for preparing an ablation-resistant resin-based fiber-reinforced composite material based on the heat confinement effect, as described in the first aspect, comprising the following steps: (a) The dispersion containing the first filler is introduced into the fiber cloth using vacuum, and then dried to obtain the modified fiber cloth; (b) The resin is coated onto the modified fiber cloth by a coating method to obtain a prepreg of the modified fiber cloth; the resin is coated onto the unmodified fiber cloth by a coating method to obtain a load-bearing inner sublayer. (c) Spray a dispersion containing a second filler onto the surface of the prepreg of the modified fiber cloth, and dry it to form an outer layer to obtain an ablation-resistant sublayer; (d) Stack the ablation-resistant sublayer and the load-bearing inner sublayer in sequence and perform hot pressing.

[0026] Further, the hot pressing method includes: pressing at 0 MPa for 15-25 min at 85-95°C; then pressing at 1 MPa for 25-35 min at 85-95°C; then pressing at 3 MPa for 25-35 min at 115-125°C; then pressing at 5 MPa for 55-65 min at 145-155°C; and then pressing at 5 MPa for 25-35 min at 175-185°C.

[0027] Further, the preparation of the dispersion containing the first filler includes: dispersing the first filler in a solvent, stirring, and ultrasonicating. Further, the solvent includes isopropanol and water.

[0028] Further, the preparation of the dispersion containing the second filler includes: dispersing the second filler in a solvent, stirring, and ultrasonicating. Further, the solvent includes isopropanol and water.

[0029] Furthermore, in the dispersion containing the first filler, the dispersion concentration of the first filler is 10~30wt%; in the dispersion containing the second filler, the dispersion concentration of the second filler is 10~30wt%.

[0030] Compared with the prior art, the beneficial effects of the present invention are as follows: The composite material of this invention features a first filler layer within the fiber voids of the prepreg layer, forming a one-dimensional filling pattern that provides radial thermal pathways to the material. A second filler layer forms a two-dimensional coating on the surface of the prepreg layer, providing axial thermal pathways. Together, they construct a three-dimensional induced heat transfer network. This structure not only avoids disordered filler filling but also, based on the principle of multi-dimensional heat induction, constructs ordered thermal pathways and gradients within the material, achieving a heat confinement effect and significantly improving the material's heat dissipation capacity, high-temperature carbonization performance, and resistance to thermal shock. Consequently, the composite material's ablation resistance is enhanced in multiple dimensions, and the upper limit of its temperature tolerance is significantly increased. Simultaneously, it reduces the decrease in mechanical properties caused by filler filling and allows the material to maintain good mechanical strength after ablation, achieving a synergistic improvement in both mechanical properties and ablation resistance. Attached Figure Description

[0031] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0032] Figure 1This is a schematic diagram of the structure of a plate made of ablation-resistant resin-based fiber-reinforced composite material according to an embodiment of the present invention; Figure 2 This is a schematic diagram of another ablation-resistant resin-based fiber-reinforced composite material plate provided in an embodiment of the present invention; Figure 3 A schematic diagram of the structure of another ablation-resistant resin-based fiber-reinforced composite material plate provided in an embodiment of the present invention; Figure 4 A schematic diagram of the structure of another ablation-resistant resin-based fiber-reinforced composite material plate provided in an embodiment of the present invention; Figure 5 This is a photograph of the ablation-resistant resin-based fiber-reinforced composite material plate obtained in Example 3 of the present invention.

[0033] Figure label: 10 - First ablation-resistant sublayer; 20 - Second ablation-resistant sublayer; 30 - Bearing inner sublayer; 11, 21 - Fiber cloth; 12, 22 - First filler; 13, 23 - Second filler. Detailed Implementation

[0034] The technical solution of the present invention will be clearly and completely described below with reference to the accompanying drawings and specific embodiments. However, those skilled in the art will understand that the embodiments described below are some embodiments of the present invention, but not all embodiments, and are only used to illustrate the present invention, and should not be regarded as limiting the scope of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall be followed. Where the manufacturers of reagents or instruments are not specified, they are all conventional products that can be purchased commercially.

[0035] In a first aspect, the present invention provides an ablation-resistant resin-based fiber-reinforced composite material based on the heat confinement effect, comprising an ablation-resistant layer; the ablation-resistant layer comprises an alternately stacked first ablation-resistant sublayer and ablation-resistant sublayer; Both the first ablation-resistant sublayer and the second ablation-resistant sublayer include a prepreg layer and an outer layer disposed on at least one side surface of the prepreg layer; The prepreg layer is a prepreg of modified fiber cloth, and the modified fiber cloth is a fiber cloth filled with a first filler; the outer layer contains a second filler. The first filler and the second filler in the first ablation-resistant sublayer and the second ablation-resistant sublayer are each independently selected from either thermally conductive filler or thermally insulating filler.

[0036] The composite material of this invention features a first filler layer within the fiber voids of the prepreg layer, forming a one-dimensional filling pattern that provides radial thermal pathways and enhances the composite material's charring performance at high temperatures. The outer layer formed by the second filler layer on the surface of the prepreg layer constitutes a two-dimensional coating pattern, providing axial thermal pathways and improving the composite material's resistance to thermal shock. Together, these two fillers construct a three-dimensional induced heat transfer network, regulating the heat dissipation process within the material and preventing localized damage caused by excessive local heat. This structure not only avoids disordered filler filling but also, based on the principle of multi-dimensional heat induction, constructs ordered thermal pathways and gradients within the material, achieving a heat confinement effect and significantly improving the material's heat dissipation capacity, high-temperature charring performance, and resistance to thermal shock. The heat confinement in this invention refers to the gradient difference in thermal conductivity within the composite material caused by its structural design, resulting in a relative concentration of heat in high-conductivity regions, thus forming a heat confinement effect. As a result, the ablation resistance of the composite material is enhanced in multiple dimensions, and the upper limit of the temperature resistance is significantly improved. At the same time, the composite material of the present invention reduces the mechanical property decline caused by filler filling and enables the material to maintain good mechanical strength after ablation, thus achieving a synergistic improvement in mechanical properties and ablation resistance.

[0037] In some embodiments, the total number of stacked layers of the first ablation-resistant sublayer and the second ablation-resistant sublayer is 14 to 70 layers, specifically a range of 14, 18, 20, 30, 40, 50, 60, 65, 70 layers or any combination thereof.

[0038] In some embodiments, the first filler and the second filler in the first ablation-resistant sublayer are each independently selected from either a thermally conductive filler or a thermally insulating filler; the first filler and the second filler in the second ablation-resistant sublayer are each independently selected from either a thermally conductive filler or a thermally insulating filler. That is, the first filler in the first ablation-resistant sublayer and the first filler in the second ablation-resistant sublayer can both be thermally conductive fillers, both be thermally insulating fillers, or both be thermally conductive fillers and thermally insulating fillers, respectively; the second filler in the first ablation-resistant sublayer and the second filler in the second ablation-resistant sublayer can both be thermally conductive fillers, both be thermally insulating fillers, or both be thermally conductive fillers and thermally insulating fillers, respectively.

[0039] In some embodiments, in the first ablation-resistant sublayer, both the first filler and the second filler are thermally conductive fillers; or, both the first filler and the second filler are thermally insulating fillers; or, the first filler is a thermally conductive filler and the second filler is a thermally insulating filler; or, the first filler is a thermally insulating filler and the second filler is a thermally conductive filler.

[0040] In some embodiments, in the second ablation-resistant sublayer, both the first filler and the second filler are thermally conductive fillers; or, both the first filler and the second filler are thermally insulating fillers; or, the first filler is a thermally conductive filler and the second filler is a thermally insulating filler; or, the first filler is a thermally insulating filler and the second filler is a thermally conductive filler.

[0041] The thermally conductive filler of the present invention is a functional filler with a thermal coefficient higher than 10 W / m·K; the thermally insulating filler is a functional filler with a thermal coefficient lower than 0.1 W / m·K.

[0042] In subsequent specific embodiments of the present invention, an outer layer is provided only on one side surface of the prepreg layer.

[0043] Figure 1 This is a schematic diagram of the structure of a plate of ablation-resistant resin-based fiber-reinforced composite material provided in an embodiment of the present invention. It includes several alternating layers of a first ablation-resistant sublayer 10 and a second ablation-resistant sublayer 20. The modified fiber cloth of the first ablation-resistant sublayer 10 is a fiber cloth 11 filled with a first filler 12, which is a thermally conductive filler; the outer layer of the first ablation-resistant sublayer 10 contains a second filler 13, which is also a thermally conductive filler. The modified fiber cloth of the second ablation-resistant sublayer 20 is a fiber cloth 21 filled with a first filler 22, which is also a thermally conductive filler; the outer layer of the second ablation-resistant sublayer 20 contains a second filler 23, which is also a thermally conductive filler.

[0044] Figure 2 This is a schematic diagram of another ablation-resistant resin-based fiber-reinforced composite material plate provided in an embodiment of the present invention, comprising several alternating layers of a first ablation-resistant sublayer 10 and a second ablation-resistant sublayer 20. The modified fiber cloth of the first ablation-resistant sublayer 10 is a fiber cloth 11 filled with a first filler 12, which is a thermally conductive filler; the outer layer of the first ablation-resistant sublayer 10 contains a second filler 13, which is a thermally insulating filler. The modified fiber cloth of the second ablation-resistant sublayer 20 is a fiber cloth 21 filled with a first filler 22, which is a thermally conductive filler; the outer layer of the second ablation-resistant sublayer 20 contains a second filler 23, which is a thermally insulating filler.

[0045] Figure 3This is a schematic diagram of the structure of another ablation-resistant resin-based fiber-reinforced composite material plate provided in an embodiment of the present invention, comprising several alternatingly stacked first ablation-resistant sublayers 10 and 20. The modified fiber cloth of the first ablation-resistant sublayer 10 is a fiber cloth 11 filled with a first filler 12, which is a thermally insulating filler; the outer layer of the first ablation-resistant sublayer 10 contains a second filler 13, which is also a thermally insulating filler. The modified fiber cloth of the second ablation-resistant sublayer 20 is a fiber cloth 21 filled with a first filler 22, which is also a thermally conductive filler; the outer layer of the second ablation-resistant sublayer 20 contains a second filler 23, which is also a thermally conductive filler.

[0046] In some embodiments, the insulating filler includes, but is not limited to, silicon dioxide, and the thermally conductive filler includes, but is not limited to, at least one of boron nitride, silicon carbide, and boron carbide.

[0047] In some embodiments, the first filler and the second filler are each independently selected from either a surface-modified thermally conductive filler or a thermally insulating filler.

[0048] In some embodiments, the particle size of the first filler and the second filler is 50nm~200μm, specifically it can be a range of 50nm, 100nm, 300nm, 500nm, 800nm, 1μm, 10μm, 50μm, 100μm, 150μm, 200μm or any combination thereof.

[0049] In some embodiments, in the first or second ablation-resistant sublayer, the total mass of the first filler and the second filler is 20% to 40% of the mass of the fiber cloth, specifically within the range of 20%, 25%, 30%, 35%, 40%, or any combination thereof; wherein, the mass of the fiber cloth refers to the initial mass of the fiber cloth before modification (e.g., before filling with the first filler), and unless otherwise specified, subsequent references to the mass of the fiber cloth refer to the initial mass of the fiber cloth. Controlling the total mass of the first and second fillers in the ablation-resistant sublayer within the above range is beneficial for balancing the mechanical properties and ablation resistance of the composite material.

[0050] In some embodiments, in the first ablation-resistant sublayer or the second ablation-resistant sublayer, the mass of the first filler is 10% to 20% of the mass of the fiber cloth, specifically within the range of 10%, 12%, 15%, 18%, 20%, or any combination thereof. Adjusting the amount of the first filler within the above range ensures that the first filler effectively constructs a thermally conductive / insulating network while maintaining good mechanical properties of the composite material.

[0051] In some embodiments, in the first or second ablation-resistant sublayer, the mass of the second filler is 10% to 20% of the mass of the fiber cloth, specifically within the range of 10%, 12%, 15%, 18%, 20%, or any combination thereof. Adjusting the amount of the second filler within the above range ensures efficient two-dimensional thermal induction of the outer layer constructed with the second filler while maintaining interfacial bonding strength and good mechanical properties.

[0052] In some embodiments, the mass ratio of the fiber cloth to the resin in the prepreg layer is (6.5~7.5):(3.5~2.5).

[0053] In some embodiments, the resin used for the prepreg layer is a thermosetting resin. Further, the thermosetting resin includes at least one of epoxy resin and phenolic resin.

[0054] In some embodiments, the thickness of the prepreg layer is 0.20~0.22 mm.

[0055] In some embodiments, the fiber cloth includes, but is not limited to, at least one of basalt fiber cloth, carbon fiber cloth, and glass fiber cloth.

[0056] In some embodiments, the fiber fabric includes, but is not limited to, plain-weave fiber fabric.

[0057] In some embodiments, the ablation-resistant resin-based fiber-reinforced composite material further includes a load-bearing inner layer; the ablation-resistant layer is disposed on both sides of the load-bearing inner layer. Introducing a load-bearing inner layer in the middle of the ablation-resistant layer can, on the one hand, adjust the thickness of the composite material, and on the other hand, form a heat-confining structure with the ablation-resistant layers on both sides, thereby improving the mechanical properties and ablation resistance of the composite material.

[0058] In some embodiments, the bearing inner layer includes at least one bearing inner layer sublayer. Further, the number of the bearing inner layer sublayer accounts for 14% to 85% of the total number of the first ablation-resistant sublayer, the second ablation-resistant sublayer, and the bearing inner layer sublayer, specifically within the range of 14%, 20%, 28%, 35%, 45%, 55%, 65%, 75%, 85%, or any combination thereof.

[0059] In some embodiments, the supporting inner sublayer comprises a prepreg of unmodified fiber cloth. The type of unmodified fiber cloth may be the same as that used in modified fiber cloth, and the type of resin used to prepare the prepreg of the unmodified fiber cloth may also be the same as that used in the prepreg of the modified fiber cloth.

[0060] In some embodiments, adjacent inner support sublayers are stacked to form the inner support layer, and the ablation-resistant layers are respectively disposed on two opposite outer sides of the inner support layer. Further, the ablation-resistant layers are symmetrically disposed on two opposite outer sides of the inner support layer.

[0061] Figure 4 A schematic diagram of another ablation-resistant resin-based fiber-reinforced composite material plate provided in an embodiment of the present invention includes an ablation-resistant layer and a load-bearing inner layer, with the ablation-resistant layer disposed on both sides of the load-bearing inner layer. The ablation-resistant layer includes several alternating layers of first ablation-resistant sublayers 10 and second ablation-resistant sublayers 20. The load-bearing inner layer includes several stacked load-bearing inner layer sublayers 30.

[0062] In some embodiments, the ablation-resistant layer and / or the load-bearing inner layer are bonded together by hot pressing.

[0063] In a second aspect, the present invention provides a method for preparing an ablation-resistant resin-based fiber-reinforced composite material as provided in the first aspect, comprising the following steps: (a) The dispersion containing the first filler is introduced into the fiber cloth using vacuum, and then dried to obtain the modified fiber cloth; (b) The resin is coated onto the modified fiber cloth by a coating method to obtain a prepreg of the modified fiber cloth; (c) Spray a dispersion containing a second filler onto the surface of the prepreg of the modified fiber cloth, and dry it to form an outer layer to obtain an ablation-resistant sublayer; (d) The ablation-resistant sublayers are stacked alternately and hot-pressed.

[0064] The present invention provides another method for preparing an ablation-resistant resin-based fiber-reinforced composite material as described in the first aspect, comprising the following steps: (a) The dispersion containing the first filler is introduced into the fiber cloth using vacuum, and then dried to obtain the modified fiber cloth; (b) The resin is coated onto the modified fiber cloth by a coating method to obtain a prepreg of the modified fiber cloth; the resin is coated onto the unmodified fiber cloth by a coating method to obtain a load-bearing inner sublayer. (c) Spray a dispersion containing a second filler onto the surface of the prepreg of the modified fiber cloth, and dry it to form an outer layer to obtain an ablation-resistant sublayer; (d) Stack the ablation-resistant sublayer and the load-bearing inner sublayer in sequence and perform hot pressing.

[0065] In some embodiments, step (a), the method of introducing the dispersion containing the first filler into the fiber cloth using vacuum may include: laying the fiber cloth as a filter medium on the surface of a filtration funnel (such as a Buchner funnel), activating the vacuum system of the filtration device; uniformly applying the dispersion containing the first filler into the filtration funnel, and under negative pressure, the first filler filling into the internal voids of the fiber cloth. The above process can be performed using a conventional filtration device including a filtration funnel, a filtration flask, and a vacuum system.

[0066] In some embodiments, step (a) includes drying. Further, the drying temperature is 55-65°C.

[0067] In some embodiments, step (b) uses a conventional prepreg preparation method, which will not be described in detail here. In the obtained prepreg, the mass ratio of the fiber cloth to the resin is (6.5~7.5):(3.5~2.5), such as 7:3.

[0068] In some embodiments, the surface spraying method in step (c) includes, but is not limited to, air spraying, such as spraying with a spray bottle.

[0069] In some embodiments, step (c) includes drying. Further, the drying temperature is 55-65°C.

[0070] In some embodiments, step (d) employs a staged heating process for the hot pressing. Further, the hot pressing method includes: pressing at 0 MPa for 15-25 minutes at 85-95°C; then pressing at 1 MPa for 25-35 minutes at 85-95°C; then pressing at 3 MPa for 25-35 minutes at 115-125°C; then pressing at 5 MPa for 55-65 minutes at 145-155°C; and finally pressing at 5 MPa for 25-35 minutes at 175-185°C. In practice, the hot pressing is performed using a conventional hot press.

[0071] In some embodiments, the preparation of the dispersion containing the first filler includes: dispersing the first filler in a solvent, stirring, and sonicating. Further, the solvent includes isopropanol and water.

[0072] In some embodiments, the dispersion containing the first filler has a dispersion concentration of 10 to 30 wt%, specifically 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, or any combination thereof.

[0073] In some embodiments, the isopropanol content in the solvent of the dispersion containing the first filler is 10-50 wt%, specifically 10 wt%, 20 wt%, 30 wt%, 40 wt%, 50 wt%, or any combination thereof.

[0074] In some implementations, the ultrasonic treatment time is more than 1 hour, specifically a range of 1 hour, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, or any combination thereof.

[0075] In some embodiments, the preparation of the dispersion containing the second filler includes: dispersing the second filler in a solvent, stirring, and sonicating. Further, the solvent includes isopropanol and water.

[0076] In some embodiments, the dispersion concentration of the second filler in the dispersion containing the second filler is 10-30 wt%, specifically 10 wt%, 15 wt%, 20 wt%, 25 wt%, 30 wt%, or any combination thereof.

[0077] In some embodiments, the isopropanol content in the solvent of the dispersion containing the second filler is 10-50 wt%, specifically 10 wt%, 20 wt%, 30 wt%, 40 wt%, 50 wt%, or any combination thereof.

[0078] The above preparation method can modify the first filler and / or the second filler to obtain surface hydroxylated fillers, which improves the dispersibility of the fillers. This not only helps to reduce the amount added while ensuring ablation resistance, but also reduces material interface damage and increases interfacial bonding performance.

[0079] The following specific embodiments further illustrate the objectives and advantages of the present invention, but these embodiments should not be considered as limitations of the present invention. Some of the raw material information used in the following specific embodiments may be as follows, but is not limited thereto.

[0080] Plain woven fabric: basalt fiber, 150tex monofilament, 800D bundle, manufactured by Sichuan Glass Co., Ltd. Boron nitride: Hexagonal boron nitride, purity 99.9%, Shanghai Maclean Biochemical Technology Co., Ltd., particle size distribution 200nm~500μm; Silicon carbide: 99.9% purity, Xi'an Boer New Materials Co., Ltd., particle size distribution 0.1~120μm; Boron carbide: 99.9% purity, Shanghai Bike New Materials Technology Co., Ltd., average particle size 60nm; Silica: 99.7% purity, Shanghai Huijing Asia Nanomaterials Co., Ltd., particle size distribution 2~5μm; Phenolic resin: 80% solid content, Shandong Shengquan New Material Co., Ltd.

[0081] Example 1 This embodiment provides a method for preparing an ablation-resistant resin-based fiber-reinforced composite material plate, including the following steps: (1) Take boron nitride particles and place them in a 30% isopropanol-deionized aqueous solution to obtain a dispersion with a boron nitride particle concentration of 20wt%; then stir the dispersion at room temperature and sonicate for 4h to obtain a hydroxylated boron nitride dispersion.

[0082] (2) Lay the plain fiber fabric on the surface of the filtration funnel, start the vacuum system of the filtration device, and apply the hydroxylated boron nitride dispersion obtained in step (1) evenly to the filtration funnel. Under negative pressure, the hydroxylated boron nitride fills the internal gaps of the plain fiber fabric. Then, dry the plain fiber fabric in a 60°C oven to remove the solvent and obtain the modified plain fiber fabric. In the modified plain fiber fabric, the mass of boron nitride is 10% of the mass of the initial plain fiber fabric.

[0083] (3) Using a 150μm spiral coating rod, phenolic resin is coated onto the surfaces of two PET films to form resin films. Then, the resin films are stacked in the order of resin film-modified fiber plain weave fabric obtained in step (2)-resin film (PET film facing out) and pressed together to obtain modified fiber prepreg. In the modified fiber prepreg, the mass ratio of the initial fiber plain weave fabric to resin (based on solid content) is 7:3. The hydroxylated boron nitride dispersion obtained in step (1) is sprayed onto the surface of the modified fiber prepreg using a spray bottle, and then placed in a 60℃ oven to dry and remove the solvent to obtain an ablation-resistant sublayer. In the ablation-resistant sublayer, the total mass of boron nitride is 20% of the mass of the initial fiber plain weave fabric.

[0084] (4) Stack the 14 ablation-resistant sublayers obtained in step (3), and then place them in a hot press for hot pressing to obtain an ablation-resistant resin-based fiber-reinforced composite material plate. The hot pressing includes: pressing at 90°C and 0MPa for 20 min; then pressing at 90°C and 1MPa for 30 min; then pressing at 120°C and 3MPa for 30 min; then pressing at 150°C and 5MPa for 60 min; then pressing at 180°C and 5MPa for 30 min. After the pressing is completed, the plate is naturally cooled to room temperature and then removed.

[0085] Example 2 This embodiment refers to the preparation method of the ablation-resistant resin-based fiber-reinforced composite material plate of Example 1. The only difference is that in step (1), silicon carbide particles of equal weight are used to replace boron nitride particles in Example 1. All other aspects are the same as in Example 1.

[0086] In step (2), the mass of silicon carbide in the modified fiber plain weave fabric is 10% of the mass of the initial fiber plain weave fabric; in step (3), the total mass of silicon carbide in the ablation-resistant sublayer is 20% of the mass of the initial fiber plain weave fabric.

[0087] Example 3 This embodiment refers to the preparation method of the ablation-resistant resin-based fiber-reinforced composite material plate of Example 1. The only difference is that in step (1), boron carbide particles of equal weight are used to replace boron nitride particles in Example 1. All other aspects are the same as in Example 1.

[0088] In step (2), the mass of boron carbide in the modified fiber plain weave fabric is 10% of the mass of the initial fiber plain weave fabric; in step (3), the total mass of boron carbide in the ablation-resistant sublayer is 20% of the mass of the initial fiber plain weave fabric.

[0089] Example 4 This embodiment refers to the preparation method of the ablation-resistant resin-based fiber-reinforced composite material plate of Example 1. The only difference is that in step (1), the same weight of silica particles are used to replace the boron nitride particles of Example 1. All other aspects are the same as in Example 1.

[0090] In step (2), the mass of silica in the modified fiber plain weave fabric is 10% of the mass of the initial fiber plain weave fabric; in step (3), the total mass of silica in the ablation-resistant sublayer is 20% of the mass of the initial fiber plain weave fabric.

[0091] Example 5 This embodiment provides a method for preparing an ablation-resistant resin-based fiber-reinforced composite material plate, including the following steps: (1) Take boron nitride particles and place them in a 30% isopropanol-deionized aqueous solution to obtain a dispersion with a boron nitride particle concentration of 20wt%; then stir the dispersion at room temperature and sonicate for 4h to obtain a hydroxylated boron nitride dispersion.

[0092] (2) Lay the plain fiber fabric on the surface of the filtration funnel, start the vacuum system of the filtration device, and apply the hydroxylated boron nitride dispersion obtained in step (1) evenly to the filtration funnel. Under negative pressure, the hydroxylated boron nitride fills the internal gaps of the plain fiber fabric. Then, dry the plain fiber fabric in a 60°C oven to remove the solvent and obtain the modified plain fiber fabric. In the modified plain fiber fabric, the mass of boron nitride is 10% of the mass of the initial plain fiber fabric.

[0093] (3) Using a 150μm spiral coating rod, phenolic resin is coated onto the surface of two PET films to form a resin film. Then, the resin film, modified fiber plain weave fabric obtained in step (2), and resin film are stacked in sequence (PET film facing out) and pressed together to obtain a modified fiber prepreg. In the modified fiber prepreg, the mass ratio of the initial fiber plain weave fabric to the resin (based on solid content) is 7:3. Following the same method, the resin film, unmodified fiber plain weave fabric, and resin film are stacked in sequence (PET film facing out) and pressed together to obtain a carrier inner layer. In the carrier inner layer, the mass ratio of the initial fiber plain weave fabric (unmodified fiber plain weave fabric) to the resin (based on solid content) is 7:3. The hydroxylated boron nitride dispersion obtained in step (1) is sprayed onto the surface of the modified fiber prepreg using a spray bottle, and then placed in a 60℃ oven to dry and remove the solvent to obtain an ablation-resistant sublayer. In the ablation-resistant sublayer, the total mass of boron nitride is 20% of the mass of the initial fiber plain weave fabric.

[0094] (4) Stack the layers in the following order: 2 ablation-resistant sublayers, 10 load-bearing inner sublayers, and 2 ablation-resistant sublayers. Then, place the layers in a hot press for hot pressing to obtain an ablation-resistant resin-based fiber-reinforced composite material plate. The hot pressing process includes: pressing at 90°C and 0MPa for 20 minutes; then pressing at 90°C and 1MPa for 30 minutes; then pressing at 120°C and 3MPa for 30 minutes; then pressing at 150°C and 5MPa for 60 minutes; then pressing at 180°C and 5MPa for 30 minutes. After the pressing is completed, allow the material to cool naturally to room temperature before removing it from the press.

[0095] Example 6 This embodiment refers to the preparation method of the ablation-resistant resin-based fiber-reinforced composite material plate of Example 5, the only difference being the stacking method in step (4), the rest is the same as in Example 5. The specific differences are as follows: Step (4) of this embodiment includes: stacking the sublayers in the order of 4 ablation-resistant sublayers, 6 load-bearing inner sublayers, and 4 ablation-resistant sublayers, and then placing them in a hot press for hot pressing to obtain an ablation-resistant resin-based fiber-reinforced composite material plate.

[0096] Example 7 This embodiment refers to the preparation method of the ablation-resistant resin-based fiber-reinforced composite material plate of Example 5, the only difference being the stacking method in step (4), the rest is the same as in Example 5. The specific differences are as follows: Step (4) of this embodiment includes: stacking 6 ablation-resistant sublayers, 2 load-bearing inner sublayers, and 6 ablation-resistant sublayers in sequence, and then placing them in a hot press for hot pressing to obtain an ablation-resistant resin-based fiber-reinforced composite material plate.

[0097] Example 8 This embodiment refers to the preparation method of the ablation-resistant resin-based fiber-reinforced composite material plate of Example 5. The only difference is that in step (1), the same weight of silica particles are used to replace the boron nitride particles of Example 5. All other aspects are the same as in Example 5.

[0098] In step (2), the mass of silica in the modified fiber plain weave fabric is 10% of the mass of the initial fiber plain weave fabric; in step (3), the total mass of silica in the ablation-resistant sublayer is 20% of the mass of the initial fiber plain weave fabric.

[0099] Example 9 This embodiment refers to the preparation method of the ablation-resistant resin-based fiber-reinforced composite material plate of Example 6. The only difference is that in step (1), the same weight of silica particles are used to replace the boron nitride particles of Example 6. All other aspects are the same as in Example 6.

[0100] In step (2), the mass of silica in the modified fiber plain weave fabric is 10% of the mass of the initial fiber plain weave fabric; in step (3), the total mass of silica in the ablation-resistant sublayer is 20% of the mass of the initial fiber plain weave fabric.

[0101] Example 10 This embodiment refers to the preparation method of the ablation-resistant resin-based fiber-reinforced composite material plate of Example 7. The only difference is that in step (1), the same weight of silicon dioxide particles are used to replace the boron nitride particles of Example 7. All other aspects are the same as in Example 7.

[0102] In step (2), the mass of silica in the modified fiber plain weave fabric is 10% of the mass of the initial fiber plain weave fabric; in step (3), the total mass of silica in the ablation-resistant sublayer is 20% of the mass of the initial fiber plain weave fabric.

[0103] Example 11 This embodiment provides a method for preparing an ablation-resistant resin-based fiber-reinforced composite material plate, including the following steps: (1) Boron nitride particles were placed in a 30% isopropanol-deionized aqueous solution to obtain a dispersion with a boron nitride particle concentration of 20 wt%. The dispersion was then stirred and sonicated at room temperature for 4 h to obtain a hydroxylated boron nitride dispersion. Silica particles were placed in a 30% isopropanol-deionized aqueous solution to obtain a dispersion with a silica particle concentration of 20 wt%. The dispersion was then stirred and sonicated at room temperature for 4 h to obtain a hydroxylated silica dispersion.

[0104] (2) Lay the plain fiber fabric on the surface of the filtration funnel, start the vacuum system of the filtration device, and apply the hydroxylated boron nitride dispersion obtained in step (1) evenly to the filtration funnel. Under negative pressure, the hydroxylated boron nitride fills the internal gaps of the plain fiber fabric. Then, dry the plain fiber fabric in a 60°C oven to remove the solvent and obtain the modified plain fiber fabric. In the modified plain fiber fabric, the mass of boron nitride is 10% of the mass of the initial plain fiber fabric.

[0105] (3) Using a 150μm spiral coating rod, phenolic resin is coated onto the surfaces of two PET films to form a resin film. Then, the resin film, modified fiber plain weave fabric obtained in step (2), and resin film are stacked in sequence (PET film facing out) and pressed together to obtain a modified fiber prepreg. In the modified fiber prepreg, the mass ratio of the initial fiber plain weave fabric to the resin (based on solid content) is 7:3. The hydroxylated silica dispersion obtained in step (1) is sprayed onto the surface of the modified fiber prepreg using a spray bottle, and then placed in a 60℃ oven to dry and remove the solvent to obtain an ablation-resistant sublayer. In the ablation-resistant sublayer, the mass of silica is 10% of the mass of the initial fiber plain weave fabric.

[0106] (4) Stack the 14 ablation-resistant sublayers obtained in step (3), and then place them in a hot press for hot pressing to obtain an ablation-resistant resin-based fiber-reinforced composite material plate. The hot pressing includes: pressing at 90°C and 0MPa for 20 min; then pressing at 90°C and 1MPa for 30 min; then pressing at 120°C and 3MPa for 30 min; then pressing at 150°C and 5MPa for 60 min; then pressing at 180°C and 5MPa for 30 min. After the pressing is completed, the plate is naturally cooled to room temperature and then removed.

[0107] Example 12 This embodiment provides a method for preparing an ablation-resistant resin-based fiber-reinforced composite material plate, including the following steps: (1) Boron nitride particles were placed in a 30% isopropanol-deionized aqueous solution to obtain a dispersion with a boron nitride particle concentration of 20 wt%. The dispersion was then stirred and sonicated at room temperature for 4 h to obtain a hydroxylated boron nitride dispersion. Silica particles were placed in a 30% isopropanol-deionized aqueous solution to obtain a dispersion with a silica particle concentration of 20 wt%. The dispersion was then stirred and sonicated at room temperature for 4 h to obtain a hydroxylated silica dispersion.

[0108] (2) Lay the fiber plain weave cloth on the surface of the suction filter funnel, start the vacuum system of the suction filter device, and apply the hydroxylated silica dispersion obtained in step (1) evenly to the suction filter funnel. Under negative pressure, the hydroxylated silica fills the internal gaps of the fiber plain weave cloth. Then, dry the fiber plain weave cloth in a 60°C oven to remove the solvent and obtain the modified fiber plain weave cloth. In the modified fiber plain weave cloth, the mass of silica is 10% of the mass of the initial fiber plain weave cloth.

[0109] (3) Using a 150μm spiral coating rod, phenolic resin is coated onto the surfaces of two PET films to form a resin film. Then, the resin film, modified fiber plain weave fabric obtained in step (2), and resin film are stacked in the order of resin film - modified fiber plain weave fabric - resin film (PET film facing out) and pressed together to obtain modified fiber prepreg. In the modified fiber prepreg, the mass ratio of the initial fiber plain weave fabric to the resin (based on solid content) is 7:3. The hydroxylated boron nitride dispersion obtained in step (1) is sprayed onto the surface of the modified fiber prepreg using a spray bottle, and then placed in a 60℃ oven to dry and remove the solvent to obtain an ablation-resistant sublayer. In the ablation-resistant sublayer, the mass of boron nitride is 10% of the mass of the initial fiber plain weave fabric.

[0110] (4) Stack the 14 ablation-resistant sublayers obtained in step (3), and then place them in a hot press for hot pressing to obtain an ablation-resistant resin-based fiber-reinforced composite material plate. The hot pressing includes: pressing at 90°C and 0MPa for 20 min; then pressing at 90°C and 1MPa for 30 min; then pressing at 120°C and 3MPa for 30 min; then pressing at 150°C and 5MPa for 60 min; then pressing at 180°C and 5MPa for 30 min. After the pressing is completed, the plate is naturally cooled to room temperature and then removed.

[0111] Example 13 This embodiment provides a method for preparing an ablation-resistant resin-based fiber-reinforced composite material plate, including the following steps: (1) Boron nitride particles were placed in a 30% isopropanol-deionized aqueous solution to obtain a dispersion with a boron nitride particle concentration of 20 wt%. The dispersion was then stirred and sonicated at room temperature for 4 h to obtain a hydroxylated boron nitride dispersion. Silica particles were placed in a 30% isopropanol-deionized aqueous solution to obtain a dispersion with a silica particle concentration of 20 wt%. The dispersion was then stirred and sonicated at room temperature for 4 h to obtain a hydroxylated silica dispersion.

[0112] (2) Lay the plain fiber fabric on the surface of the filtration funnel, start the vacuum system of the filtration device, and apply the hydroxylated boron nitride dispersion obtained in step (1) evenly to the filtration funnel. Under negative pressure, the hydroxylated boron nitride fills the internal gaps of the plain fiber fabric. Then, dry the plain fiber fabric in a 60°C oven to remove the solvent and obtain the modified plain fiber fabric. In the modified plain fiber fabric, the mass of boron nitride is 10% of the mass of the initial plain fiber fabric.

[0113] The fiber plain weave cloth is laid on the surface of the suction filter funnel. The vacuum system of the suction filter device is started, and the hydroxylated silica dispersion obtained in step (1) is uniformly applied to the suction filter funnel. Under negative pressure, the hydroxylated silica fills the internal voids of the fiber plain weave cloth. Then the fiber plain weave cloth is dried in a 60°C oven to remove the solvent and obtain the modified fiber plain weave cloth. In the modified fiber plain weave cloth, the mass of silica is 10% of the mass of the initial fiber plain weave cloth.

[0114] (3) Using a 150μm spiral coating rod, phenolic resin is coated onto the surfaces of two PET films to form a resin film. Then, the resin film, modified fiber plain weave fabric (filled with boron nitride) obtained in step (2), and resin film are stacked in the order of resin film - modified fiber plain weave fabric (filled with boron nitride) - resin film (PET film facing out) and pressed together to obtain the first modified fiber prepreg. In the first modified fiber prepreg, the mass ratio of the initial fiber plain weave fabric to the resin (based on solid content) is 7:3. The hydroxylated boron nitride dispersion obtained in step (1) is sprayed onto the surface of the first modified fiber prepreg using a spray bottle, and then placed in a 60℃ oven to dry and remove the solvent to obtain the first ablation-resistant sublayer. In the first ablation-resistant sublayer, the total mass of boron nitride is 20% of the mass of the initial fiber plain weave fabric.

[0115] Phenolic resin was coated onto the surfaces of two PET films using a 150 μm spiral coating rod to form resin films. The resin films were then stacked in the order of resin film – modified fiber plain weave fabric (filled with silica) obtained in step (2) – resin film (PET films facing outwards) and pressed together to obtain a second modified fiber prepreg. In the second modified fiber prepreg, the mass ratio of the initial fiber plain weave fabric to the resin (based on solid content) was 7:3. The hydroxylated silica dispersion obtained in step (1) was sprayed onto the surface of the second modified fiber prepreg using a spray bottle, and then dried in a 60°C oven to remove the solvent, resulting in a second ablation-resistant sublayer. In the second ablation-resistant sublayer, the total mass of silica was 20% of the mass of the initial fiber plain weave fabric.

[0116] (4) The first ablation-resistant sublayer and the second ablation-resistant sublayer are stacked alternately for a total of 14 layers, and then placed in a hot press for hot pressing to obtain an ablation-resistant resin-based fiber-reinforced composite material plate. The hot pressing includes: pressing at 90°C and 0MPa for 20 min; then pressing at 90°C and 1MPa for 30 min; then pressing at 120°C and 3MPa for 30 min; then pressing at 150°C and 5MPa for 60 min; then pressing at 180°C and 5MPa for 30 min. After the pressing is completed, the plate is naturally cooled to room temperature and then removed.

[0117] Comparative Example 1 Comparative Example 1 provides a method for preparing a resin-based fiber-reinforced composite material plate, comprising the following steps: (1) Phenolic resin is coated onto the surface of two PET films using a 150μm spiral coating rod to form a resin film. Then, the resin film, fiber plain weave cloth, and resin film are stacked in the order of resin film-fiber plain weave cloth-resin film (PET film facing out) and pressed together to obtain fiber prepreg. In the fiber prepreg, the mass ratio of the initial fiber plain weave cloth to the resin (in terms of solid content) is 7:3.

[0118] (2) Stack the 14 layers of fiber prepreg obtained in step (1) and then place them in a hot press for hot pressing to obtain a resin-based fiber reinforced composite material plate. The hot pressing includes: pressing at 90°C and 0MPa for 20 min; then pressing at 90°C and 1MPa for 30 min; then pressing at 120°C and 3MPa for 30 min; then pressing at 150°C and 5MPa for 60 min; then pressing at 180°C and 5MPa for 30 min. After the pressing is completed, the plate is naturally cooled to room temperature and then removed.

[0119] Comparative Example 2 Comparative Example 2 provides a method for preparing a resin-based fiber-reinforced composite material plate, comprising the following steps: (1) Take boron nitride particles and place them in a 30% isopropanol-deionized aqueous solution to obtain a dispersion with a boron nitride particle concentration of 20wt%; then stir the dispersion at room temperature and sonicate for 4h to obtain a hydroxylated boron nitride dispersion.

[0120] (2) Lay the plain fiber fabric on the surface of the filtration funnel, start the vacuum system of the filtration device, and apply the hydroxylated boron nitride dispersion obtained in step (1) evenly to the filtration funnel. Under negative pressure, the hydroxylated boron nitride fills the internal gaps of the plain fiber fabric. Then, dry the plain fiber fabric in a 60°C oven to remove the solvent and obtain the modified plain fiber fabric. In the modified plain fiber fabric, the mass of boron nitride is 10% of the mass of the initial plain fiber fabric.

[0121] (3) Use a 150μm spiral coating rod to coat the phenolic resin onto the surface of two PET films to form a resin film. Then, stack the resin film, modified fiber plain weave fabric obtained in step (2), and resin film in sequence (PET film facing out) and press them together to obtain modified fiber prepreg. In the modified fiber prepreg, the mass ratio of the initial fiber plain weave fabric to the resin (in terms of solid content) is 7:3.

[0122] (4) Stack the 14 layers of modified fiber prepreg obtained in step (3), and then place them in a hot press for hot pressing to obtain a resin-based fiber reinforced composite material plate. The hot pressing includes: pressing at 90°C and 0MPa for 20 min; then pressing at 90°C and 1MPa for 30 min; then pressing at 120°C and 3MPa for 30 min; then pressing at 150°C and 5MPa for 60 min; then pressing at 180°C and 5MPa for 30 min. After the pressing is completed, the plate is naturally cooled to room temperature and then removed.

[0123] Comparative Example 3 Comparative Example 3 was prepared by the same method as Comparative Example 2, except that in step (1), silicon carbide particles of equal weight were used to replace boron nitride particles in Comparative Example 2. All other steps were the same as Comparative Example 2.

[0124] In step (2), the mass of silicon carbide in the modified fiber plain weave fabric is 10% of the mass of the initial fiber plain weave fabric.

[0125] Comparative Example 4 Comparative Example 4 was prepared by the same method as Comparative Example 2, except that in step (1), boron carbide particles of equal weight were used to replace boron nitride particles in Comparative Example 2. All other steps were the same as Comparative Example 2.

[0126] In step (2), the mass of boron carbide in the modified fiber plain weave fabric is 10% of the mass of the initial fiber plain weave fabric.

[0127] Comparative Example 5 Comparative Example 5 was prepared by the same method as Comparative Example 2, except that in step (1), silicon dioxide particles of equal weight were used to replace boron nitride particles in Comparative Example 2.

[0128] In step (2), the mass of silica in the modified fiber plain weave fabric is 10% of the mass of the initial fiber plain weave fabric.

[0129] Comparative Example 6 Comparative Example 6 provides a method for preparing a resin-based fiber-reinforced composite material plate, comprising the following steps: (1) Take boron nitride particles and place them in a 30% isopropanol-deionized aqueous solution to obtain a dispersion with a boron nitride particle concentration of 20wt%; then stir the dispersion at room temperature and sonicate for 4h to obtain a hydroxylated boron nitride dispersion.

[0130] (2) Using a 150μm spiral coating rod, phenolic resin is coated onto the surfaces of two PET films to form resin films. Then, the resin films are stacked in the order of resin film-fiber plain weave fabric-resin film (PET films facing out) and pressed together to obtain fiber prepreg. In the fiber prepreg, the mass ratio of the initial fiber plain weave fabric to the resin (based on solid content) is 7:3. The hydroxylated boron nitride dispersion obtained in step (1) is sprayed onto the surface of the fiber prepreg using a spray bottle, and then placed in a 60℃ oven to dry and remove the solvent to obtain modified prepreg. In the modified prepreg, the mass of boron nitride is 10% of the mass of the initial fiber plain weave fabric.

[0131] (3) Stack the 14 layers of modified prepreg obtained in step (2) and then place them in a hot press for hot pressing to obtain a resin-based fiber-reinforced composite material plate. The hot pressing includes: pressing at 90°C and 0MPa for 20 min; then pressing at 90°C and 1MPa for 30 min; then pressing at 120°C and 3MPa for 30 min; then pressing at 150°C and 5MPa for 60 min; then pressing at 180°C and 5MPa for 30 min. After the pressing is completed, the plate is naturally cooled to room temperature and then removed.

[0132] Comparative Example 7 Comparative Example 7 was prepared by the same method as Comparative Example 6, except that in step (1), silicon carbide particles of equal weight were used to replace boron nitride particles in Comparative Example 6. All other steps were the same as those in Comparative Example 6.

[0133] In step (2), the mass of silicon carbide in the modified prepreg is 10% of the mass of the initial fiber plain weave fabric.

[0134] Comparative Example 8 Comparative Example 8 follows the same method as Comparative Example 6 for preparing resin-based fiber-reinforced composite material flat plates, except that in step (1), boron carbide particles of equal weight are used to replace boron nitride particles in Comparative Example 6, and the rest are the same as Comparative Example 6.

[0135] In step (2), the mass of boron carbide in the modified prepreg is 10% of the mass of the initial fiber plain weave fabric.

[0136] Comparative Example 9 Comparative Example 9 was prepared by the same method as Comparative Example 6, except that in step (1), silicon dioxide particles of equal weight were used to replace boron nitride particles in Comparative Example 6. All other steps were the same as Comparative Example 6.

[0137] In step (2), the mass of silica in the modified prepreg is 10% of the mass of the initial fiber plain weave fabric.

[0138] Comparative Example 10 Comparative Example 10 provides a method for preparing a resin-based fiber-reinforced composite material plate, comprising the following steps: (1) Take boron nitride particles and place them in a 30% isopropanol-deionized aqueous solution to obtain a dispersion with a boron nitride particle concentration of 20wt%; then stir the dispersion at room temperature and sonicate for 4h to obtain a hydroxylated boron nitride dispersion.

[0139] (2) Lay the plain fiber fabric on the surface of the filtration funnel, start the vacuum system of the filtration device, and apply the hydroxylated boron nitride dispersion obtained in step (1) evenly to the filtration funnel. Under negative pressure, the hydroxylated boron nitride fills the internal gaps of the plain fiber fabric. Then, dry the plain fiber fabric in a 60°C oven to remove the solvent and obtain the modified plain fiber fabric. In the modified plain fiber fabric, the mass of boron nitride is 10% of the mass of the initial plain fiber fabric.

[0140] (3) Using a 150μm spiral coating rod, phenolic resin is coated onto the surfaces of two PET films to form a resin film. Then, the resin film, modified fiber plain weave fabric obtained in step (2), and resin film are stacked in sequence (PET film facing out) and pressed together to obtain a modified fiber prepreg. In the modified fiber prepreg, the mass ratio of the initial fiber plain weave fabric to the resin (based on solid content) is 7:3. Following the same method, the resin film, unmodified fiber plain weave fabric, and resin film are stacked in sequence (PET film facing out) and pressed together to obtain a carrier inner layer. In the carrier inner layer, the mass ratio of the initial fiber plain weave fabric (unmodified fiber plain weave fabric) to the resin (based on solid content) is 7:3.

[0141] (4) Stack the modified fiber prepreg, 10 load-bearing inner sublayers, and 2 layers of modified fiber prepreg in sequence, and then place them in a hot press for hot pressing to obtain an ablation-resistant resin-based fiber-reinforced composite material plate. The hot pressing process includes: pressing at 90°C and 0MPa for 20 min; then pressing at 90°C and 1MPa for 30 min; then pressing at 120°C and 3MPa for 30 min; then pressing at 150°C and 5MPa for 60 min; then pressing at 180°C and 5MPa for 30 min. After the process is completed, allow it to cool naturally to room temperature before removing it.

[0142] Comparative Example 11 Comparative Example 11 follows the same preparation method as Comparative Example 10 for resin-based fiber-reinforced composite material flat plates, except that the stacking method in step (4) is different; all other steps are the same as in Comparative Example 10. The specific differences are as follows: Step (4) of this comparative example includes: stacking 4 layers of modified fiber prepreg, 6 layers of bearing inner sublayer, and 4 layers of modified fiber prepreg in sequence, and then placing them in a hot press for hot pressing to obtain a resin-based fiber reinforced composite material plate.

[0143] Comparative Example 12 Comparative Example 12 follows the same preparation method as Comparative Example 10 for resin-based fiber-reinforced composite material flat plates, except that the stacking method in step (4) is different; all other steps are the same as in Comparative Example 10. The specific differences are as follows: Step (4) of this comparative example includes: stacking 6 layers of modified fiber prepreg, 2 layers of bearing inner sublayer, and 6 layers of modified fiber prepreg in sequence, and then placing them in a hot press for hot pressing to obtain a resin-based fiber reinforced composite material plate.

[0144] Comparative Example 13 Comparative Example 13 provides a method for preparing a resin-based fiber-reinforced composite material plate, comprising the following steps: (1) Take boron nitride particles and place them in a 30% isopropanol-deionized aqueous solution to obtain a dispersion with a boron nitride particle concentration of 20wt%; then stir the dispersion at room temperature and sonicate for 4h to obtain a hydroxylated boron nitride dispersion.

[0145] (2) Using a 150μm spiral coating rod, phenolic resin is coated onto the surfaces of two PET films to form resin films. Then, the resin films are stacked in the order of resin film-fiber plain weave fabric-resin film (PET films facing out) and pressed together to obtain fiber prepreg. In the fiber prepreg, the mass ratio of the initial fiber plain weave fabric to the resin (based on solid content) is 7:3. The hydroxylated boron nitride dispersion obtained in step (1) is sprayed onto the surface of the fiber prepreg using a spray bottle, and then placed in a 60℃ oven to dry and remove the solvent to obtain modified prepreg. In the modified prepreg, the mass of boron nitride is 10% of the mass of the initial fiber plain weave fabric.

[0146] (3) Stack the prepregs in the order of 2 layers of modified fiber, 10 layers of fiber prepreg, and 2 layers of modified fiber prepreg, and then place them in a hot press for hot pressing to obtain a resin-based fiber-reinforced composite material plate. The hot pressing process includes: pressing at 90°C and 0MPa for 20 min; then pressing at 90°C and 1MPa for 30 min; then pressing at 120°C and 3MPa for 30 min; then pressing at 150°C and 5MPa for 60 min; then pressing at 180°C and 5MPa for 30 min. After the process is completed, the plate is naturally cooled to room temperature and then removed.

[0147] Comparative Example 14 Comparative Example 14 follows the same preparation method as Comparative Example 13 for resin-based fiber-reinforced composite material flat plates, except that the stacking method in step (4) is different; all other steps are the same as in Comparative Example 13. The specific differences are as follows: Step (4) of this comparative example includes: stacking 4 layers of modified fiber prepreg, 6 layers of fiber prepreg, and 4 layers of modified fiber prepreg in sequence, and then placing them in a hot press for hot pressing to obtain a resin-based fiber reinforced composite material flat plate.

[0148] Comparative Example 15 Comparative Example 15 follows the same preparation method as Comparative Example 13 for resin-based fiber-reinforced composite material flat plates, except that the stacking method in step (4) is different; all other steps are the same as in Comparative Example 13. The specific differences are as follows: Step (4) of this comparative example includes: stacking 6 layers of modified fiber prepreg, 2 layers of fiber prepreg, and 6 layers of modified fiber prepreg in sequence, and then placing them in a hot press for hot pressing to obtain a resin-based fiber reinforced composite material flat plate.

[0149] Comparative Example 16 Comparative Example 16 was prepared by the same method as Comparative Example 10, except that in step (1), silicon dioxide particles of equal weight were used to replace boron nitride particles in Comparative Example 10. All other steps were the same as Comparative Example 10.

[0150] In step (2), the mass of silica in the modified fiber plain weave fabric is 10% of the mass of the initial fiber plain weave fabric.

[0151] Comparative Example 17 Comparative Example 17 follows the same preparation method as Comparative Example 16 for resin-based fiber-reinforced composite material flat plates, except that the stacking method in step (4) is different; all other steps are the same as in Comparative Example 16. The specific differences are as follows: Step (4) of this comparative example includes: stacking 4 layers of modified fiber prepreg, 6 layers of bearing inner sublayer, and 4 layers of modified fiber prepreg in sequence, and then placing them in a hot press for hot pressing to obtain a resin-based fiber reinforced composite material plate.

[0152] Comparative Example 18 Comparative Example 18 follows the same preparation method as Comparative Example 16 for resin-based fiber-reinforced composite material flat plates, except that the stacking method in step (4) is different; all other steps are the same as in Comparative Example 16. The specific differences are as follows: Step (4) of this comparative example includes: stacking 6 layers of modified fiber prepreg, 2 layers of bearing inner sublayer, and 6 layers of modified fiber prepreg in sequence, and then placing them in a hot press for hot pressing to obtain a resin-based fiber reinforced composite material plate.

[0153] Comparative Example 19 Comparative Example 19 was prepared by the same method as Comparative Example 13, except that in step (1), silicon dioxide particles of equal weight were used to replace boron nitride particles in Comparative Example 13, and the rest were the same as Comparative Example 13.

[0154] In step (2), the mass of boron nitride in the modified prepreg is 10% of the mass of the initial fiber plain weave fabric.

[0155] Comparative Example 20 Comparative Example 20 follows the same preparation method as Comparative Example 19 for resin-based fiber-reinforced composite material flat plates, except that the stacking method in step (4) is different; all other steps are the same as in Comparative Example 19. The specific differences are as follows: Step (4) of this comparative example includes: stacking 4 layers of modified fiber prepreg, 6 layers of fiber prepreg, and 4 layers of modified fiber prepreg in sequence, and then placing them in a hot press for hot pressing to obtain a resin-based fiber reinforced composite material flat plate.

[0156] Comparative Example 21 Comparative Example 21 follows the same preparation method as Comparative Example 19 for resin-based fiber-reinforced composite material flat plates, except that the stacking method in step (4) is different; all other steps are the same as in Comparative Example 19. The specific differences are as follows: Step (4) of this comparative example includes: stacking 6 layers of modified fiber prepreg, 2 layers of fiber prepreg, and 6 layers of modified fiber prepreg in sequence, and then placing them in a hot press for hot pressing to obtain a resin-based fiber reinforced composite material flat plate.

[0157] Experimental Example To compare and illustrate the ablation resistance of composite materials prepared in different embodiments and comparative examples, the thickness of composite materials in different embodiments and comparative examples was tested. Then, oxy-acetylene ablation tests were conducted on the composite materials in accordance with GJB 323B-2018 "Test Method for Ablation of Ablation Materials". The back surface temperature of the composite materials was tested after 5 seconds and 10 seconds of ablation. The test results are shown in Table 1.

[0158] Table 1 Test results of different composite materials

[0159] The tensile strength (GB / T 1447-2005 "Test Method for Tensile Properties of Fiber Reinforced Plastics") and flexural strength (GB / T 1449-2005 "Test Method for Flexural Properties of Fiber Reinforced Plastics") of the composite materials of different embodiments and comparative examples were further tested. The tensile strength and flexural strength of the composite materials after ablation for 5 seconds according to the above-mentioned oxy-acetylene ablation test were also tested. The test results are shown in Table 2.

[0160] Table 2. Test results of mechanical properties of different composite materials

[0161] The test results above show that the composite material of this invention constructs a three-dimensional induced heat transfer network, regulates the heat dissipation process within the material, avoids localized damage caused by excessive local heat, and significantly improves the material's heat dissipation capacity, high-temperature carbonization performance, and resistance to thermal shock. Simultaneously, the composite material of this invention reduces the mechanical property degradation caused by filler filling and maintains good mechanical strength after ablation, achieving a synergistic improvement in mechanical properties and ablation resistance.

[0162] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. An ablation-resistant resin-based fiber-reinforced composite material based on the heat confinement effect, characterized in that, Includes an ablation-resistant layer; the ablation-resistant layer comprises alternating stacked first and second ablation-resistant sublayers; Both the first ablation-resistant sublayer and the second ablation-resistant sublayer include a prepreg layer and an outer layer disposed on at least one side surface of the prepreg layer; The prepreg layer is a prepreg of modified fiber cloth, and the modified fiber cloth is a fiber cloth filled with a first filler; the outer layer contains a second filler. The first filler and the second filler in the first ablation-resistant sublayer and the second ablation-resistant sublayer are each independently selected from either thermally conductive filler or thermally insulating filler.

2. The ablation-resistant resin-based fiber-reinforced composite material according to claim 1, characterized in that, The total number of stacked layers of the first ablation-resistant sublayer and the second ablation-resistant sublayer is 14 to 70. Preferably, the first filler and the second filler in the first ablation-resistant sublayer are each independently selected from either a thermally conductive filler or a thermally insulating filler; the first filler and the second filler in the second ablation-resistant sublayer are each independently selected from either a thermally conductive filler or a thermally insulating filler.

3. The ablation-resistant resin-based fiber-reinforced composite material according to claim 1, characterized in that, It has at least one of the following characteristics: (1) In the first ablation-resistant sublayer or the second ablation-resistant sublayer, the total mass of the first filler and the second filler is 20% to 40% of the mass of the fiber cloth; (2) In the first ablation-resistant sublayer or the second ablation-resistant sublayer, the mass of the first filler is 10% to 20% of the mass of the fiber cloth; (3) In the first ablation-resistant sublayer or the second ablation-resistant sublayer, the mass of the second filler is 10% to 20% of the mass of the fiber cloth; (4) The heat-insulating filler includes silicon dioxide, and the heat-conducting filler includes at least one of boron nitride, silicon carbide and boron carbide; (5) The first filler and the second filler are each independently selected from either the thermally conductive filler and the thermally insulating filler that have undergone surface modification treatment.

4. The ablation-resistant resin-based fiber-reinforced composite material according to claim 1, characterized in that, It has at least one of the following characteristics: (1) In the prepreg layer, the mass ratio of the fiber cloth to the resin is (6.5~7.5): (3.5~2.5); (2) The thickness of the prepreg layer is 0.20~0.22mm; (3) The resin used in the prepreg layer is a thermosetting resin; (4) The fiber cloth includes at least one of basalt fiber cloth, carbon fiber cloth and glass fiber cloth.

5. The ablation-resistant resin-based fiber-reinforced composite material according to claim 1, characterized in that, It also includes a bearing inner layer; the ablation-resistant layer is disposed on both sides of the bearing inner layer.

6. The ablation-resistant resin-based fiber-reinforced composite material according to claim 5, characterized in that, The inner load-bearing layer includes at least one inner load-bearing layer sublayer; Preferably, the number of the supporting inner sublayer accounts for 14% to 85% of the total number of the first ablation-resistant sublayer, the second ablation-resistant sublayer, and the supporting inner sublayer; Preferably, the supporting inner sublayer comprises a prepreg of unmodified fiber cloth; Preferably, the adjacent inner load-bearing sublayers are stacked to form the inner load-bearing layer, and the ablation-resistant layers are respectively disposed on two opposite outer sides of the inner load-bearing layer; Preferably, the ablation-resistant layer and / or the load-bearing inner layer are composited by hot pressing.

7. The method for preparing the ablation-resistant resin-based fiber-reinforced composite material according to any one of claims 1 to 4, characterized in that, Includes the following steps: (a) The dispersion containing the first filler is introduced into the fiber cloth using vacuum, and then dried to obtain the modified fiber cloth; (b) The resin is coated onto the modified fiber cloth by a coating method to obtain a prepreg of the modified fiber cloth; (c) Spray a dispersion containing a second filler onto the surface of the prepreg of the modified fiber cloth, and dry it to form an outer layer to obtain an ablation-resistant sublayer; (d) The ablation-resistant sublayers are stacked alternately and hot-pressed.

8. The method for preparing the ablation-resistant resin-based fiber-reinforced composite material according to any one of claims 5 to 6, characterized in that, Includes the following steps: (a) The dispersion containing the first filler is introduced into the fiber cloth using vacuum, and then dried to obtain the modified fiber cloth; (b) The resin is coated onto the modified fiber cloth by a coating method to obtain a prepreg of the modified fiber cloth; the resin is coated onto the unmodified fiber cloth by a coating method to obtain a load-bearing inner sublayer. (c) Spray a dispersion containing a second filler onto the surface of the prepreg of the modified fiber cloth, and dry it to form an outer layer to obtain an ablation-resistant sublayer; (d) The ablation-resistant sublayer and the load-bearing inner sublayer are stacked in sequence and then hot-pressed.

9. The method for preparing the ablation-resistant resin-based fiber-reinforced composite material according to claim 7 or 8, characterized in that, The hot pressing method includes: pressing at 0 MPa for 15-25 min at 85-95°C; then pressing at 1 MPa for 25-35 min at 85-95°C; then pressing at 3 MPa for 25-35 min at 115-125°C; then pressing at 5 MPa for 55-65 min at 145-155°C; and then pressing at 5 MPa for 25-35 min at 175-185°C.

10. The method for preparing the ablation-resistant resin-based fiber-reinforced composite material according to claim 7 or 8, characterized in that, It has at least one of the following characteristics: (1) The preparation of the dispersion containing the first filler includes: dispersing the first filler in a solvent, stirring and ultrasonically treating it; the solvent includes isopropanol and water; (2) The preparation of the dispersion containing the second filler includes: dispersing the second filler in a solvent, stirring and ultrasonically treating it; the solvent includes isopropanol and water; (3) In the dispersion containing the first filler, the dispersion concentration of the first filler is 10~30 wt%; (4) In the dispersion containing the second filler, the dispersion concentration of the second filler is 10~30wt%.

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