Fiber-reinforced ablative composite panel and method of making same

Abstract

The application discloses a kind of fiber reinforced ablation-resistant composite board and preparation method thereof.Fiber yarn is twisted, and then woven into fiber reinforced cloth according to the warp and weft staggered weaving method, impregnated after being placed in resin, and then cured, and the method is obtained.The method uses twisting weaving process, on the one hand, it ensures the integration of the composite board forming, greatly improves the thickness and density of the fiber reinforced cloth, on the other hand, it also improves the expandability of the composite board, the amount of twisted fiber yarn and the winding diameter can be controlled to quantitatively control the thickness of single-layer fabric, further, the mechanical properties of the composite board in different stress directions can be further strengthened by weaving angle.The composite board obtained by the above preparation method is light weight and high strength, has excellent ablation resistance and good mechanical properties.

Description

TECHNICAL FIELD

[0001] The present application relates to an ablation-resistant composite plate, in particular to a fiber-reinforced ablation-resistant composite plate and a preparation method thereof, and belongs to the field of fiber-reinforced composite materials. BACKGROUND

[0002] At present, with the further use and promotion of composite materials in the field of aerospace, a part of ablation-resistant composite materials has been widely used in the field of aerospace due to their light weight, good mechanical properties and good high-temperature ablation resistance. In the early use, metal materials, as traditional materials, were initially used as ablation-resistant core components due to their mature processing technology. With the improvement of composite material forming process, and in order to further reduce the overall weight of the product, reduce energy consumption, and ensure good ablation performance of the material and easy replacement of the ablation component.

[0003] Chinese patent CN 110804274A discloses a light heat-proof composite material based on a spacer structure fabric reinforcement and a preparation method thereof. The material adopts a face-core functional gradient structure. The face layer is a dense material mainly providing heat dissipation and load bearing capacity, and the core is a porous material mainly playing the role of low density and heat insulation. The reinforcement in the material system is a fabric preform with a spacer three-dimensional structure of pure inorganic fibers or organic / inorganic hybrid fibers. The overall structure of the patent is a spacer structure, which adopts multiple layers of fabric linked by link fiber bundles to form a hollow structure. However, in order to achieve the designed thickness, multiple layers of lamination must be used. The composite plate formed after vacuum infusion of multiple layers of lamination has weak interlayer bonding and is easy to expand and delaminate under heat. Only through interlayer weaving can the delamination and cracking during high-temperature ablation be avoided.

[0004] In addition, some related institutions use short-cut fiber sheet molding. However, due to the short length of the short-cut fibers, the continuity of the fibers is poor, resulting in poor high-temperature performance of the whole. SUMMARY

[0005] In view of the problems existing in the prior art, the first object of the present application is to provide a fiber-reinforced ablation-resistant composite plate. The fiber reinforcement in the composite plate adopts a twisting process, and the thickness of a single layer is 3-10 mm, which effectively avoids high-temperature delamination. After strengthening, the obtained composite plate has overall light weight, excellent ablation resistance, and after being subjected to a high-temperature particle flow ablation at a temperature of 1500-2000℃ for 5-10 s, the back temperature at the ablation center is below 120℃.

[0006] The second object of the present application is to provide a preparation method of the fiber-reinforced ablation-resistant composite plate, which can control the thickness of the single-layer fabric by controlling the amount of twisted fiber filaments and the winding diameter, and can strengthen the mechanical properties of the composite plate in different stress directions by the weaving angle.

[0007] To achieve the above technical objects, the present application provides a preparation method of the fiber-reinforced ablation-resistant composite plate, which twists the fiber filaments and weaves them into a fiber-reinforced cloth according to the warp and weft interlacing mode, or twists the fiber filaments and mixes them with the reinforcing filaments according to the warp and weft interlacing mode to weave into a fiber-reinforced cloth; the fiber-reinforced cloth is fully impregnated in resin and then solidified, or the upper surface and / or the lower surface of the fiber-reinforced cloth is overlaid with a reinforcing felt, and then fully impregnated in resin and then solidified, thereby obtaining the fiber-reinforced ablation-resistant composite plate.

[0008] The preparation method provided by the present application adopts the preparation process of twisted mixed weaving fiber filaments, which not only ensures the single-layer structure of the composite plate, but also greatly improves the high-temperature ablation-resistant performance of the material, and further, the obtained fiber-reinforced cloth after resin impregnation strengthens the mechanical strength and heat insulation performance of the composite plate, and the forming process of the method is simple, the porosity of the product after pouring is low, and the obtained composite plate has excellent high-temperature mechanical properties.

[0009] As a preferred scheme, the fiber filaments include at least one of aluminum silicate fiber filaments, aluminum oxide fiber filaments and silicon carbide fibers.

[0010] As a preferred scheme, the reinforcing filaments are at least one of stainless steel filaments, carbon fiber filaments and high-silicon oxygen fiber filaments.

[0011] As a preferred scheme, the twisting mode is double-fiber bundle unidirectional winding twisting and / or single-fiber bundle unidirectional winding twisting. Further preferably, the twisting mode of the radially woven fiber filaments is double-fiber bundle unidirectional winding, and the twisting mode of the weft woven fiber filaments is single-fiber bundle unidirectional winding twisting.

[0012] The double-fiber bundle unidirectional winding twisting mode not only can improve the overall thickness of the fiber cloth, but also can greatly improve the strength of the material, which is used for the reinforcement of the main stress direction of the material; the single-fiber bundle unidirectional winding twisting is used to support the overall strength of the fiber cloth, to ensure that the non-main stress direction has basic mechanical strength, and to reduce the overall weight of the material.

[0013] As a preferred scheme, the double-fiber bundle unidirectional winding twisting condition is that the winding diameter is 2-10 mm and the weaving angle is 45°-90°. The fiber bundle winding diameter directly determines the thickness of the single-layer fiber cloth, and the maximum diameter of the fiber cloth is the overall diameter of the double-fiber bundle unidirectional twisted fiber.

[0014] As a preferred scheme, the single filament bundle is twisted and wound under the condition that the winding diameter is 1-5 mm and the weaving angle is 45-90°.

[0015] As a preferred scheme, the total density of the fiber reinforced cloth is 0.4-1.0 g / cm 3 .

[0016] As a preferred scheme, the carbonization rate of the resin is ≥70%, the viscosity at room temperature is 150-300 mPa·S, and the mass of the resin accounts for 5-10% of the mass of the fiber reinforced cloth. Further preferably, the resin is a phenolic resin.

[0017] The main purpose of selecting the high carbonization rate resin is to ensure that the resin reacts to form a more temperature-resistant carbonized layer under the action of high-temperature ablation gas flow. The carbonized layer can stably exist under high-temperature conditions and will not be washed away by the gas flow, thereby playing a role in protecting the internal layer from rapid ablation.

[0018] As a preferred scheme, the curing method is vacuum infusion, RTM molding or hand lay-up molding. The preferred condition for the vacuum infusion is that the pressure is controlled at 0.1 KPa negative pressure, the heating temperature is controlled at 80-150℃, and the heating time is 2-2.5 h.

[0019] The application also provides a fiber reinforced ablation-resistant composite board prepared by any of the above preparation methods.

[0020] The application adjusts the twisting method of the ceramic fiber fabric fiber, the weaving method and the curing forming method, prepares a composite board which is only formed by a single layer of fiber and phenolic resin infusion molding, can resist 1000-1500℃ for a long time, can resist 2000-3000℃ instantaneously, has the excellent properties of light weight, high strength and heat preservation, and expands the application range of the fiber reinforced phenolic resin composite board in the high-temperature ablation-resistant field.

[0021] As a preferred scheme, the thickness of the fiber reinforced ablation-resistant composite board is 3-10 mm, and the density is 0.8-1.2 g / cm 3 .

[0022] Further, the application also provides an expansion method of the composite board. The reinforcing felt is added to the upper and lower surfaces of the fiber reinforced cloth during the curing stage. The specific process is as follows:

[0023] 1) The reinforcing filaments are mixed and woven in the fiber fabric. The twisted filament diameters of the warp and weft fibers are designed according to the designed thickness. The diameter is controlled by the number of twisted fibers. The fiber filament weaving angle is designed according to the stress direction. The single layer of woven fabric can be designed according to the actual required product size. The conventional width is controlled at 1-1.5 m.

[0024] 2) according to the product structure design, the size of the blanking is designed, then the prepared fiber cloth is cut, 1 or 2 layers of reinforcing felt are appropriately laid on the upper and lower surfaces of the fiber cloth, and the fiber cloth is laid on the designed mold, then resin is impregnated according to different processes, and then heating and curing, vacuum infusion, RTM process or hand lay-up molding process are adopted; if the hand lay-up molding process is adopted, the mold needs to be pressurized, and the radial fiber tows are ensured to be consistent with the stress direction during the laying process.

[0025] As a preferred scheme, the reinforcing filaments are at least one of stainless steel filaments, carbon fiber filaments and high-silica fiber filaments.

[0026] As a preferred scheme, the reinforcing felt is at least one of glass fiber felt, carbon fiber felt, carbon fiber woven cloth and metal plate.

[0027] The mixing and weaving of the reinforcing filaments in the fiber tows can significantly improve the high-temperature mechanical strength of the product, and the addition of the reinforcing felt during the curing and forming stage can improve the overall mechanical properties by 20% to 50%, and the thermal conductivity coefficient can be increased by 5% to 10%.

[0028] The present application can solve the problems of the traditional metal ablation-resistant material, such as large weight, difficult to replace and disassemble, and the like. In addition, in the forming process of the existing continuous fibers such as carbon fibers, high-silica fibers and the like, the single-layer thickness of the fiber fabric is relatively thin, and most of the single-layer thickness of the fiber fabric is below 1 mm. Therefore, when a product with a thickness of more than 1 mm is prepared, multiple layers of laying and pasting need to be adopted. The composite board formed after the multiple layers of laying and pasting are vacuum infused has weak interlayer bonding and is easy to expand and delaminate due to heat. The delamination and cracking of the composite board during the high-temperature ablation process can be prevented only by interlayer weaving. In addition, if the chopped fiber sheet is molded, the overall high-temperature mechanical properties are weak due to the discontinuity of the fibers. Therefore, in the present application, the fiber filament twisting and mixing process is adopted, and the single-layer weaving thickness can reach 3 mm to 10 mm. The flat tensile strength of the composite product is about 20 MPa to 30 MPa, the bending strength is about 40 MPa to 50 MPa, the impact toughness is 25 KJ / m 2 ~ 35 KJ / m 2 , the density is 0.8 to 1.2 x 10 3 kg / m 3 , the thermal conductivity coefficient is controlled to be 0.13 W / (m·K), and the linear ablation thickness of the composite board after ablation for 1 min in the oxyacetylene outer flame is controlled to be less than 10%, the product does not crack, the ablation area carbonizes uniformly, and the ablation center back temperature is controlled to be less than 120℃.

[0029] Compared with the prior art, the technical scheme of the present application has the following beneficial technical effects:

[0030] 1) The ablation-resistant composite board provided by this invention allows for controllable adjustment of the thickness of a single layer of fabric, is lightweight and high-strength, and possesses excellent ablation resistance and good mechanical properties. Test results show that the tensile strength of this ablation-resistant composite board is approximately 20MPa to 30MPa, the flexural strength is approximately 40MPa to 50MPa, and the impact toughness is 25KJ / m. 2 ~35KJ / m 2 The density is between 0.8 and 1.2 × 10⁻⁶. 3 kg / m 3 The thermal conductivity is controlled at 0.13 W / (m·K), and after the composite plate is ablated by the acetylene outer flame for 1 minute, the linear ablation thickness is controlled at less than 10%, the product does not crack, the carbonization of the ablation area is uniform, and the back temperature of the ablation center is controlled at less than 120℃.

[0031] 2) In the technical solution provided by the present invention, the process of fiber twisting and warp and weft interlacing is adopted to greatly improve the thickness and density of fiber reinforced fabric. The thickness of single-layer fabric is quantitatively controlled by controlling the amount of twisted fiber and the winding diameter. Furthermore, the mechanical properties of composite board in different stress directions can be enhanced by the weaving angle.

[0032] 3) In the technical solution provided by the present invention, the preparation method of resin impregnation and curing molding ensures the integration of composite board molding on the one hand, and improves the extensibility of composite board on the other hand. During the molding process, the reinforcing felt can be adhered by resin, which further improves the mechanical properties and ablation resistance of composite board. Attached Figure Description

[0033] Figure 1 This is a schematic diagram of the composite plate obtained in Embodiment 1 of the present invention;

[0034] 1. Radial twisted fiber bundle, 2. Weft twisted fiber bundle, 3. Resin matrix material; Detailed Implementation

[0035] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, many other embodiments obtained by those skilled in the art without creative effort are all within the scope of protection of the present invention.

[0036] Example 1

[0037] The design thickness of the ablation-resistant composite board is 5 mm, the fiber filament is aluminum silicate ceramic fiber, and the fiber filament is twisted by double filament bundle unidirectional winding. The twisted fiber filament bundle has a diameter of 2.5 mm, and each fiber filament bundle is twisted by 100 ceramic fiber filaments with a diameter of 0.025 mm. The 90° / 0° warp and weft are woven, and then 4.0 kg / m 2 of phenolic resin is injected and cured to prepare a ceramic fiber reinforced ablation-resistant composite board with a thickness of 5 mm.

[0038] Test results show that the ablation-resistant composite board has a tensile strength of about 25 MPa, a bending strength of about 50 MPa, an impact toughness of 35 KJ / m 2 , a density of 0.9 x 10 3 kg / m 3 , and a thermal conductivity of 0.13 W / (m·K). After ablation in an ethylene flame for 1 min at 1500℃, the linear ablation thickness is controlled to be 8%, the product does not crack, the ablation area is uniformly carbonized, and the ablation center back temperature is 110℃.

[0039] Example 2

[0040] The design thickness of the ablation-resistant composite board is 5 mm, the fiber filament is aluminum silicate ceramic fiber, and the fiber filament is twisted by double filament bundle unidirectional winding. The twisted fiber filament bundle has a diameter of 2.5 mm, and each fiber filament bundle is twisted by 100 ceramic fiber filaments with a diameter of 0.025 mm. The 90° / 0° warp and weft are woven, and then 4.0 kg / m 2 of phenolic resin is injected and cured to prepare a ceramic fiber reinforced ablation-resistant composite board with a thickness of 5 mm. The reinforced composite board has a tensile strength of 55 MPa, a bending strength of 65 MPa, and a thermal conductivity of 0.13 W / (m·K). The added glass fiber felt can be directly carbonized at a high temperature of 1000℃, and does not cause deformation and cracking of the product.

[0041] Example 3

[0042] The preparation method is the same as that of Example 2, except that two layers of glass fiber chopped mat are added on the upper and lower sides for lamination. Compared with one layer of glass fiber chopped mat, the overall comprehensive mechanical properties are improved by 5%, and the thermal conductivity remains unchanged.

[0043] Example 4

[0044] The preparation method is the same as that of Example 2, except that one layer of 400 g / m 2 T300 carbon fiber is added on the upper and lower surfaces for composite injection. The mechanical properties of the reinforced composite board are improved by 20%, and no delamination occurs when the product is ablated by an oxygen-ethylene torch at 1500℃.

[0045] Example 5

[0046] The preparation method is the same as that of Example 1, except that the single filaments in the twisting process are changed from 100 ceramic fiber filaments with a diameter of 0.025 mm to 50 ceramic fiber filaments with a diameter of 0.025 mm and 50 T300 carbon fiber single filaments with a diameter of 0.025 mm, and the tensile strength is increased by 10%.

[0047] Example 6

[0048] The upper and lower surfaces of the ablation-resistant composite board obtained in Example 1 are formed into a multi-layer structure using a high-temperature-resistant adhesive high-silica fiber reinforced resin composite board, and additional support is added to the surface, so that the composite board can maintain good structural integrity under the impact of particle flow and gas flow at 2000°C.

[0049] Comparative Example 1

[0050] The preparation method is the same as that of Example 1, except that the fiber filaments used are glass fibers. The test shows that the ablation-resistant composite board obtained is penetrated by the flame at 900°C, and the composite board peels off.

[0051] Comparative Example 2

[0052] The preparation method is the same as that of Example 1, except that the fiber filaments are laid in a conventional manner without using the twisting process and the warp and weft interlaced weaving, and the single-layer thickness of the fiber reinforced cloth obtained is only 0.5 mm; 10 layers of fiber reinforced cloth are stacked and then impregnated with 4.0 kg / m 2 of phenolic resin for curing to prepare a ceramic fiber reinforced ablation-resistant composite board with a thickness of 5 mm. The test shows that the ablation-resistant composite board obtained is ablated by an ethyne outer flame at 1500°C for 1 min, and the composite board collapses and peels off along the interlayer gap.

Claims

1. A method of making a fiber reinforced ablative composite panel, characterized by: The fiber filaments are twisted and then woven into a fiber reinforced cloth according to the warp and weft interlacing mode, or the fiber filaments are twisted and then mixed with the reinforcing filaments according to the warp and weft interlacing mode to form a fiber reinforced cloth; The fiber reinforced cloth is placed in resin for sufficient impregnation and then cured, or the upper surface and / or lower surface of the fiber reinforced cloth is overlaid with a reinforcing felt, and then placed in resin for sufficient impregnation and then cured, thereby obtaining the fiber reinforced cloth; The twisting mode is double-filament bundle single-direction winding twisting and / or single-filament bundle single-direction winding twisting; The double-filament bundle single-direction winding twisting is performed at a winding diameter of 2-10 mm and an interlacing angle of 45-90°. The single-filament bundle single-direction winding twisting is performed at a winding diameter of 1-5 mm and an interlacing angle of 45-90°. The fiber filaments include at least one of aluminum silicate fiber filaments, aluminum oxide fiber filaments and silicon carbide fiber filaments.

2. The method for preparing a fiber-reinforced ablation-resistant composite board according to claim 1, characterized in that: The reinforcing filaments are at least one of stainless steel filaments, carbon fiber filaments and high-silica fiber filaments.

3. The preparation method of the fiber reinforced ablation-resistant composite plate according to claim 1, characterized in that: The reinforcing felt is at least one of glass fiber felt, carbon fiber felt, carbon fiber woven cloth and metal plate.

4. The method for preparing a fiber-reinforced ablation-resistant composite board according to claim 1, characterized in that: The total density of the fiber reinforced cloth is 0.4-1.0 g / cm 3 .

5. The method for preparing a fiber-reinforced ablation-resistant composite board according to claim 1, characterized in that: The resin has a carbonization rate of ≥70%, a normal temperature viscosity of 150-300 mPa·S, and a mass of 5-10% of the mass of the fiber reinforced cloth.

6. The method for preparing a fiber-reinforced ablation-resistant composite board according to claim 1, characterized in that: The curing mode is vacuum infusion, RTM molding or hand lay-up molding; the vacuum infusion is performed at a pressure control of 0.1 KPa negative pressure, a heating temperature control of 80-150℃ and a heating time of 2-2.5 h.

7. A fiber reinforced ablative composite panel, characterized by: The fiber reinforced ablation-resistant composite plate is prepared by the preparation method according to any one of claims 1-6.

8. The fiber reinforced ablative composite panel according to claim 7, wherein: The fiber reinforced ablation-resistant composite plate has a thickness of 3-10 mm and a density of 0.8-1.2 g / cm 3 .

Images