Method for producing glass fiber composite material

Abstract

The invention discloses a method for producing a high-performance glass fiber composite material, which comprises the following steps: a) preparing high-thermal-stability glass fiber which comprises the following components in parts by weight: 58-62 parts of SiO2, 22-26 parts of Al2O3, 8-12 parts of CaO, 3-5 parts of MgO and 2-4 parts of ZrO2, and carrying out melt spinning at 1350-1450 DEG C until the fiber diameter is 8-12 microns; b) surface modification: carrying out nitrogen plasma treatment, and depositing a gamma-aminopropyltriethoxysilane coating and 0.5-1.5 wt% of graphene oxide; c) preparing a modified polyimide resin matrix, and adding 2-5wt% of multi-walled carbon nanotubes and 1-3wt% of nano SiO2; and d) carrying out composite molding through a resin transfer molding process (the fiber volume fraction is 55-65%, the pressure is 0.8-1.2 MPa, and curing is carried out at 200-250 DEG C for 2-4 hours). The mass loss rate of the prepared material is as low as 3.2%, the tensile strength reaches 920 MPa, the fracture toughness is 17.0 MPa.m (1 / 2), and the material shows excellent thermal stability and mechanical properties and is suitable for the fields of aerospace and the like.

Description

Technical Field

[0001] The present invention relates to the technical field of glass fiber composites, and particularly to a method for producing glass fiber composites. Background Art

[0002] As a high-performance engineering material, the development of glass fiber reinforced plastics (GFRP) is closely related to the progress of materials science and manufacturing technology. Since the mid-20th century, GFRP has gradually moved from laboratory research to industrial applications and is widely used in fields such as aerospace, automotive manufacturing, construction engineering, and wind power generation. In the early production, E-glass fibers and thermosetting resins (such as epoxy resins, polyester resins) were mainly used, and were prepared by hand lay-up or spray-up processes. However, due to limitations in fiber strength and interfacial bonding, the performance was relatively limited. With the optimization of fiber drawing technology, resin impregnation process, and curing process, the mechanical properties and production efficiency of the composites have been significantly improved, promoting their application in high-performance structural components.

[0003] In recent years, the introduction of nanotechnology has injected new vitality into glass fiber composites. For example, by modifying the resin matrix or fiber surface with nano-fillers (such as carbon nanotubes, graphene), the interfacial bonding strength and durability have been significantly improved. At the same time, the progress of automated production technology, such as pultrusion, filament winding, and resin transfer molding (RTM), has realized the large-scale and efficient production of GFRP, further expanding its application scenarios. However, the existing production methods still have deficiencies in meeting the demanding performance requirements such as high temperature and high strength. For example, the performance attenuation caused by fiber softening or matrix degradation at high temperatures. Chinese Patent (CN111517748A) discloses a high-strength glass fiber composite material. By optimizing the ratio of glass fibers (containing 60-65 parts of SiO2, 20-25 parts of Al2O3, etc.), spinning fibers (containing PET), additives, and silica sol, a composite material with excellent thermal stability (mass loss of 3.9%-4.1%) at 1000°C is prepared. However, the softening of glass fibers and the degradation of spinning fibers at high temperatures may still lead to a decrease in mechanical properties. The glass fibers mainly consist of SiO2 and Al2O3 to form a network skeleton. Although they show a relatively low mass loss (3.9%-4.1%) at 1000°C, high temperatures may induce an increase in non-bridging oxygen or local structural rearrangement in the Si-O-Si network, resulting in a decrease in fiber rigidity and softening. The PET matrix in the spinning fibers has insufficient thermal stability, and its glass transition temperature (Tg~70-80°C) and decomposition temperature (~400°C) are much lower than the high-temperature working conditions, making it prone to molecular chain breakage and degradation, significantly reducing toughness and interfacial bonding force. Summary of the Invention

[0004] The present application provides a method for producing a high-performance glass fiber composite material, comprising the following steps:

[0005] a) Prepare glass fibers with high thermal stability, where the glass fibers contain the following components in parts by weight: 58 - 62 parts of SiO2, 22 - 26 parts of Al2O3, 8 - 12 parts of CaO, 3 - 5 parts of MgO, and 2 - 4 parts of ZrO2. They are prepared by a melt spinning process with a spinning temperature of 1350 - 1450 °C;

[0006] b) Perform surface modification on the glass fibers. Use plasma treatment combined with a silane coupling agent coating, and deposit a 0.5 - 1.5 wt% graphene oxide nanolayer on the fiber surface;

[0007] c) Prepare a modified resin matrix. The resin matrix is a polyimide resin, adding 2 - 5 wt% multi - walled carbon nanotubes and 1 - 3 wt% nano - SiO2 particles, and uniformly mixing them by ultrasonic dispersion and mechanical stirring;

[0008] d) Use a resin transfer molding process to composite - mold the modified glass fibers and the modified resin matrix. The molding pressure is 0.8 - 1.2 MPa, the curing temperature is 200 - 250 °C, and the curing time is 2 - 4 hours.

[0009] Preferably, in the preparation of the glass fibers, the melt spinning process is protected by an inert atmosphere, the spinning speed is 1000 - 1500 m / min, and the fiber diameter is controlled within 8 - 12 μm.

[0010] Preferably, in the surface modification of the glass fibers, the plasma treatment uses a nitrogen atmosphere, the power is 100 - 200 W, and the treatment time is 5 - 10 minutes; the silane coupling agent is γ - aminopropyltriethoxysilane, and the coating thickness is 50 - 100 nm.

[0011] Preferably, the deposition of the graphene oxide nanolayer uses a chemical vapor deposition process, the deposition temperature is 150 - 200 °C, and the deposition time is 30 - 60 minutes.

[0012] Preferably, the glass transition temperature of the polyimide resin is not lower than 350 °C, and the thermal decomposition temperature is not lower than 500 °C.

[0013] Preferably, in the modified resin matrix, the diameter of the multi - walled carbon nanotubes is 10 - 20 nm, and the length is 5 - 15 μm; the particle size of the nano - SiO2 particles is 20 - 50 nm.

[0014] Preferably, in the resin transfer molding process, the volume fraction of the glass fibers is controlled within 55 - 65%, and the resin injection speed is 50 - 100 mL / min.

[0015] This application significantly improves the performance of glass fiber composites by optimizing the glass fiber formula (58 - 62 parts of SiO2, 22 - 26 parts of Al2O3, 8 - 12 parts of CaO, 3 - 5 parts of MgO, 2 - 4 parts of ZrO2), surface modification (plasma treatment, silane coupling agent coating, and deposition of 0.5 - 1.5 wt% graphene oxide), modified resin matrix (adding 2 - 5 wt% multi-walled carbon nanotubes and 1 - 3 wt% nano-SiO2 to polyimide resin), and resin transfer molding process (fiber volume fraction of 55 - 65%, pressure of 0.8 - 1.2 MPa, curing at 200 - 250 °C for 2 - 4 hours). The data of Example 4 show that its mass loss rate is as low as 3.2%, the tensile strength is as high as 920 MPa, and the fracture toughness is 17.0 MPa·m^(1 / 2). Compared with the control example (mass loss rate of 3.6% - 4.8%, tensile strength of 760 - 800 MPa, fracture toughness of 13.8 - 14.5 MPa·m^(1 / 2)), it shows excellent thermal stability, mechanical strength, and durability, meeting the requirements for high-performance composites in the fields of aerospace, automotive manufacturing, etc. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] The drawings are used to provide a further understanding of the present invention and constitute a part of the specification. Together with the embodiments of the present invention, they are used to explain the present invention and do not constitute a limitation to the present invention. In the drawings:

[0017] Figure 1 It is the XRD pattern of preparing high thermal stability glass fiber in Step 1 of Example 4. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0018] In order to make the above objects, features, and advantages of the present invention more obvious and understandable, the following detailed description of the specific embodiments of the present invention will be given in conjunction with the embodiments of the specification.

[0019] Many specific details are set forth in the following description in order to fully understand the present invention. However, the present invention can also be implemented in other ways different from those described herein. Those skilled in the art can make similar generalizations without departing from the connotation of the present invention. Therefore, the present invention is not limited by the specific embodiments disclosed below.

[0020] Secondly, the so-called "one embodiment" or "embodiment" herein refers to a specific feature, structure, or characteristic that can be included in at least one implementation of the present invention. The phrase "in one embodiment" appearing in different places in this specification does not necessarily refer to the same embodiment, nor is it an independent or selectively exclusive embodiment from other embodiments.

[0021] Example 1

[0022] Step 1. Prepare high thermal stability glass fiber

[0023] Weigh 58 parts by mass of SiO2, 22 parts of Al2O3, 8 parts of CaO, 3 parts of MgO and 2 parts of ZrO2, pour them into a mixing device, stir evenly to form a raw material mixture, then place the mixture in a high-temperature furnace and melt it at 1350 °C for 2 hours. Nitrogen is introduced during the melting process to prevent oxidation. Subsequently, spin the mixture through a melt spinning device, control the spinning speed at 1000 m / min, and finally obtain glass fibers with a diameter of 8 μm.

[0024] Step Two. Surface modification of glass fibers

[0025] Place the prepared glass fibers in a plasma treatment device, and conduct surface activation treatment under a nitrogen atmosphere. Set the power to 100 W and the treatment time to 5 minutes to increase the surface roughness of the fibers. Subsequently, immerse the fibers in an ethanol solution containing γ-aminopropyltriethoxysilane (KH550), and form a silane coupling agent coating with a thickness of 50 nm on the fiber surface through dip coating and then dry it. Finally, deposit graphene oxide at 150 °C using chemical vapor deposition (CVD) technology for 30 minutes, control the content of graphene oxide at 0.5 wt%, and complete the surface modification.

[0026] Step Three. Preparation of modified resin matrix

[0027] Select polyimide resin with a glass transition temperature (Tg) of 350 °C and a thermal decomposition temperature of 500 °C as the matrix material. Add 2 wt% of multi-walled carbon nanotubes (diameter 10 nm, length 5 μm) and 1 wt% of nano-SiO2 (particle size 20 nm) to the resin. Place the mixture in an ultrasonic dispersion device and process it for 30 minutes to ensure uniform dispersion of the additives, and then stir it with a mechanical stirrer for 1 hour to obtain a modified resin matrix.

[0028] Step Four. Resin transfer molding (RTM) process: Uniformly lay the modified glass fibers in the RTM mold according to a volume fraction of 55%. After closing the mold, inject the modified resin into the mold at a speed of 50 mL / min through an injection device. Maintain the molding pressure at 0.8 MPa during the injection process. After the resin fills the mold, place the mold in an oven and cure it at 200 °C for 2 hours, then demold after cooling to obtain a high-performance glass fiber composite material.

[0029] Example 2

[0030] Step One. Preparation of glass fibers with high thermal stability

[0031] Weigh 60 parts by mass of SiO2, 24 parts of Al2O3, 10 parts of CaO, 4 parts of MgO, and 3 parts of ZrO2, mix them evenly, place the mixture in a high-temperature furnace, melt it at 1400 °C for 2.5 hours, introduce argon gas during the melting process to avoid oxidation, and then draw fibers through the melt spinning process. Set the spinning speed to 1200 m / min to obtain glass fibers with a diameter of 10 μm.

[0032] Step Two. Surface modification of glass fibers

[0033] Place the glass fibers in a plasma treatment device, treat them at a power of 150 W for 7 minutes in a nitrogen atmosphere to enhance surface activity; then, immerse the fibers in an ethanol solution containing KH550, coat a silane coupling agent coating with a thickness of 75 nm by the dip coating method, and dry it at 80 °C for 30 minutes; subsequently, deposit graphene oxide at 175 °C through the CVD process for 45 minutes, control the content of graphene oxide to be 1.0 wt%, and complete the surface modification of the fibers.

[0034] Step Three. Preparation of modified resin matrix

[0035] Select a polyimide resin with a Tg of 360 °C and a thermal decomposition temperature of 520 °C, add 3.5 wt% of multi-walled carbon nanotubes (diameter 15 nm, length 10 μm) and 2 wt% of nano-SiO2 (particle size 35 nm) to the resin, treat it with an ultrasonic dispersion device for 40 minutes, and then stir it in a mechanical stirrer at a speed of 500 rpm for 1.5 hours to ensure uniform distribution of the additives and obtain a modified resin.

[0036] Step Four. Resin Transfer Molding (RTM) process

[0037] Lay the modified glass fibers in the RTM mold at a volume fraction of 60%, inject the modified resin into the mold at an injection speed of 75 mL / min, control the molding pressure at 1.0 MPa, and after the resin completely fills the mold, place the mold in an oven and cure it at 225 °C for 3 hours. After cooling and demolding, obtain the finished composite material.

[0038] Example 3

[0039] Step One. Preparation of glass fibers with high thermal stability

[0040] Weigh 61 parts by mass of SiO2, 25 parts of Al2O3, 11 parts of CaO, 4.5 parts of MgO, and 3.5 parts of ZrO2 in proportion, mix them evenly, melt them in a high-temperature furnace at 1425 °C for 2.5 hours, introduce nitrogen gas during melting, and then draw fibers through a melt spinning device at a spinning speed of 1300 m / min to obtain glass fibers with a diameter of 11 μm.

[0041] Step 2. Surface modification of glass fiber

[0042] Place the glass fiber in a plasma treatment device under a nitrogen atmosphere and treat it at a power of 180 W for 8 minutes to activate the surface; then immerse the fiber in an ethanol solution containing KH550, coat a silane coupling agent coating with a thickness of 90 nm, and dry it at 85 °C for 40 minutes; then deposit graphene oxide by CVD process at 180 °C for 50 minutes, control the content to be 1.2 wt%, and complete the modification.

[0043] Step 3. Preparation of modified resin matrix

[0044] Select a polyimide resin with a Tg of 370 °C and a thermal decomposition temperature of 530 °C, add 4 wt% of multi-walled carbon nanotubes (diameter 18 nm, length 12 μm) and 2.5 wt% of nano-SiO2 (particle size 40 nm), disperse it by ultrasonic for 45 minutes and stir mechanically at 600 rpm for 2 hours to obtain a uniform modified resin matrix.

[0045] Step 4. Resin transfer molding (RTM) process

[0046] Place the modified glass fiber in the RTM mold at a volume fraction of 62%, inject the modified resin at a speed of 80 mL / min, set the molding pressure to 1.1 MPa, after the resin filling is completed, cure it at 230 °C for 3.5 hours, demold after cooling, and obtain the composite material.

[0047] Example 4

[0048] Step 1. Preparation of high thermal stability glass fiber

[0049] Weigh 62 parts of SiO2, 26 parts of Al2O3, 12 parts of CaO, 5 parts of MgO and 4 parts of ZrO2 by mass and mix them evenly. Melt them at 1450 °C for 3 hours, and introduce argon during the melting process to prevent oxidation. Then draw the fiber by the melt spinning process at a spinning speed of 1500 m / min to obtain glass fiber with a diameter of 12 μm.

[0050] Step 2. Surface modification of glass fiber

[0051] Place the glass fiber in a plasma treatment device under a nitrogen atmosphere and treat it at a power of 200 W for 10 minutes to optimize the surface properties; then immerse the fiber in an ethanol solution containing KH550, coat a silane coupling agent coating with a thickness of 100 nm, and dry it at 90 °C for 45 minutes; finally, deposit graphene oxide by CVD process at 200 °C for 60 minutes, control the content to be 1.5 wt%, and complete the surface modification.

[0052] Step 3. Preparation of modified resin matrix

[0053] Select a polyimide resin with a Tg of 380 °C and a thermal decomposition temperature of 550 °C, add 5 wt% of multi-walled carbon nanotubes (diameter 20 nm, length 15 μm) and 3 wt% of nano-SiO2 (particle size 50 nm), disperse ultrasonically for 50 minutes and mechanically stir at 700 rpm for 2.5 hours to obtain a uniformly dispersed modified resin.

[0054] Step Four. Resin Transfer Molding (RTM) Process

[0055] Lay the modified glass fibers in the RTM mold at a volume fraction of 65%, inject the modified resin at a speed of 100 mL / min, control the molding pressure at 1.2 MPa, and after the resin completely fills the mold, cure at 250 °C for 4 hours, and demold after cooling to obtain the composite material.

[0056] Control Example

[0057] Control Example 1

[0058] The difference between this Control Example 1 and Example 4 is that ZrO2 is removed from the glass fiber formulation and the SiO2 content is adjusted to keep the total amount unchanged.

[0059] Preparation Steps:

[0060] Glass Fiber Preparation: Weigh 66 parts of SiO2, 26 parts of Al2O3, 12 parts of CaO, 5 parts of MgO (without ZrO2), mix evenly and melt at 1450 °C for 3 hours, protect with argon, and spin at a speed of 1500 m / min to obtain glass fibers with a diameter of 12 μm.

[0061] Surface Modification: Place the fibers in a nitrogen atmosphere plasma equipment and treat at a power of 200 W for 10 minutes; immerse in KH550 ethanol solution, coat with a 100 nm thick coating, and dry at 90 °C for 45 minutes; deposit 1.5 wt% graphene oxide by CVD process at 200 °C for 60 minutes.

[0062] Modified Resin Matrix: Select a polyimide resin with a Tg of 380 °C and a thermal decomposition temperature of 550 °C, add 5 wt% multi-walled carbon nanotubes (diameter 20 nm, length 15 μm) and 3 wt% nano-SiO2 (particle size 50 nm), disperse ultrasonically for 50 minutes, and mechanically stir at 700 rpm for 2.5 hours.

[0063] Control Example 2

[0064] The difference between this control example and Example 4 is that the glass fibers are not subjected to plasma treatment, silane coupling agent coating, or graphene oxide deposition.

[0065] Preparation Steps:

[0066] Preparation of glass fiber: Weigh 62 parts of SiO2, 26 parts of Al2O3, 12 parts of CaO, 5 parts of MgO, and 4 parts of ZrO2, melt at 1450 °C for 3 hours under argon protection, and spin at 1500 m / min to obtain fibers with a diameter of 12 μm.

[0067] Surface modification: Omit plasma treatment, KH550 coating, and graphene oxide deposition, and directly use unmodified fibers.

[0068] Modified resin matrix: Select a polyimide resin with a Tg of 380 °C and a thermal decomposition temperature of 550 °C, add 5 wt% multi-walled carbon nanotubes (diameter 20 nm, length 15 μm) and 3 wt% nano-SiO2 (particle size 50 nm), ultrasonically disperse for 50 minutes, and stir at 700 rpm for 2.5 hours.

[0069] RTM process: The fiber volume fraction is 65%, inject the resin at 100 mL / min, the pressure is 1.2 MPa, cure at 250 °C for 4 hours, and cool to demold.

[0070] Comparative Example 3

[0071] The difference between this comparative example and Example 4 is that multi-walled carbon nanotubes and nano-SiO2 are not added to the polyimide resin.

[0072] Preparation steps:

[0073] Preparation of glass fiber: Weigh 62 parts of SiO2, 26 parts of Al2O3, 12 parts of CaO, 5 parts of MgO, and 4 parts of ZrO2, melt at 1450 °C for 3 hours under argon protection, and spin at 1500 m / min to obtain fibers with a diameter of 12 μm.

[0074] Surface modification: Treat the fibers with 200 W plasma in a nitrogen atmosphere for 10 minutes, coat with a 100 nm KH550 coating, and dry at 90 °C for 45 minutes; deposit 1.5 wt% graphene oxide by CVD process at 200 °C for 60 minutes.

[0075] Modified resin matrix: Select a polyimide resin with a Tg of 380 °C and a thermal decomposition temperature of 550 °C, do not add any nano-fillers, and only ensure the resin is uniform by mechanical stirring for 2.5 hours.

[0076] RTM process: The fiber volume fraction is 65%, inject the resin at 100 mL / min, the pressure is 1.2 MPa, cure at 250 °C for 4 hours, and cool to demold.

[0077] Performance test method

[0078] 1. Mass loss rate: Test according to standard ASTM E1131;

[0079] 2. Tensile strength: Tested in accordance with standard ASTM D3039;

[0080] 3. Fracture toughness: Tested in accordance with standard ASTM E399.

[0081] Table 1

[0082]

[0083] Combined with Example 4 and Figure 1 It can be seen that after the glass fiber with the formulation of 62 parts of SiO2, 26 parts of Al2O3, 12 parts of CaO, 5 parts of MgO and 4 parts of ZrO2 is prepared by melt spinning at 1450 °C, it presents an amorphous structure and contains a trace amount of crystalline phase, including mullite (3Al2O3·2SiO2), anorthite (CaAl2Si2O8), zircon (ZrSiO4) and spinel (MgAl2O4). Mullite strengthens the glass skeleton through a three-dimensional network structure, reduces the formation of non-bridging oxygen at high temperatures to improve thermal stability and rigidity; anorthite forms chemical bonds with resin functional groups through Ca 2+ and Al 3+ to optimize the interfacial bonding force to enhance tensile strength and fracture toughness; zircon reduces corrosion damage due to the high chemical stability of ZrO2 and reduces the mass loss rate; spinel improves the thermal expansion matching through the solid solution of Mg 2+ and Al 3+ to reduce the thermal stress during high-temperature curing, and significantly improves the thermal stability mass loss rate, tensile strength and fracture toughness of the composite material.

[0084] Combined with Examples 1 to 4 and Table 1, it can be seen that the mass loss rate of the high-performance glass fiber composites prepared in Examples 1 to 4 is between 3.2% and 3.8%, the tensile strength is between 820 and 920 MPa, and the fracture toughness is between 15.2 and 17.0 MPa·m^(1 / 2).

[0085] Combined with Example 4, Comparative Example 1 and Table 1, it can be seen that the performance comparison between Example 4 and Comparative Example 1 shows that the mass loss rate of Example 4 (3.2%) is lower than that of Comparative Example 1 (4.8%), the tensile strength (920 MPa) is higher than that of Comparative Example 1 (780 MPa), and the fracture toughness (17.0 MPa·m^(1 / 2)) is better than that of Comparative Example 1 (14.2 MPa·m^(1 / 2)); ZrO2 in Example 4 improves the chemical stability of the glass network by forming zircon (ZrSiO4) crystalline phase, reduces the formation of non-bridging oxygen and structural rearrangement of the Si-O-Si network at high temperatures, enhances thermal stability, thereby reducing the mass loss rate. At the same time, the solid solution strengthening effect of ZrO2 improves the fiber rigidity and significantly improves the tensile strength and fracture toughness.

[0086] Combined with Example 4, Comparative Example 2 and Table 1, it can be seen that the performance comparison between Example 4 and Comparative Example 2 shows that the mass loss rate of Example 4 (3.2%) is lower than that of Comparative Example 2 (4.0%), the tensile strength (920 MPa) is higher than that of Comparative Example 2 (760 MPa), and the fracture toughness (17.0 MPa·m^(1 / 2)) is better than that of Comparative Example 2 (13.8 MPa·m^(1 / 2)); the surface modification of Example 4 increases the surface roughness and active sites of the fiber through plasma treatment, the silane coupling agent (KH550) forms a chemical bond bridge on the fiber surface, and the graphene oxide nanolayer further enhances the interfacial adhesion force, thereby improving the interfacial bonding strength between the glass fiber and the polyimide resin matrix, reducing interfacial slippage and thermal degradation, and at the same time improving the stress transfer efficiency (increasing the tensile strength and fracture toughness).

[0087] Combined with Example 4, Comparative Example 3 and Table 1, it can be seen that the performance comparison between Example 4 and Comparative Example 3 shows that the mass loss rate of Example 4 (3.2%) is lower than that of Comparative Example 3 (3.6%), the tensile strength (920 MPa) is higher than that of Comparative Example 3 (800 MPa), and the fracture toughness (17.0 MPa·m^(1 / 2)) is better than that of Comparative Example 3 (14.5 MPa·m^(1 / 2)); in Example 4, multi-walled carbon nanotubes (diameter 20 nm, length 15 μm) form a network structure in the resin matrix through their high strength and excellent thermal conductivity, enhancing the rigidity and thermal stability of the matrix, reducing thermal degradation during high-temperature curing (250 °C, 4 hours) (reducing the mass loss rate), and nano-SiO2 particles (particle size 50 nm) improve the crack resistance of the matrix through filling matrix micropores and dispersion strengthening, synergistically improving the stress transfer efficiency (increasing the tensile strength and fracture toughness).

[0088] The above are only the preferred embodiments of the present invention and are not used to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements for some of the technical features. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A method for producing high-performance glass fiber composites, characterized in that, Including the following steps: a) Prepare high thermal stability glass fibers, the glass fibers comprising the following components in parts by weight: 58 - 62 parts of SiO2, 22 - 26 parts of Al2O3, 8 - 12 parts of CaO, 3 - 5 parts of MgO, 2 - 4 parts of ZrO2, prepared by a melt spinning process, and the spinning temperature is 1350 - 1450 °C; b) Carry out surface modification on the glass fibers, using plasma treatment combined with a silane coupling agent coating, and deposit a 0.5 - 1.5 wt% graphene oxide nano-layer on the fiber surface; c) Prepare a modified resin matrix, the resin matrix being a polyimide resin, adding 2 - 5 wt% multi-walled carbon nanotubes and 1 - 3 wt% nano-SiO2 particles, and uniformly mixing by ultrasonic dispersion and mechanical stirring; d) Adopt a resin transfer molding process to composite and mold the modified glass fibers and the modified resin matrix, with a molding pressure of 0.8 - 1.2 MPa, a curing temperature of 200 - 250 °C, and a curing time of 2 - 4 hours.

2. The method according to claim 1, wherein In the preparation of the glass fibers, the melt spinning process is protected by an inert atmosphere, the spinning speed is 1000 - 1500 m / min, and the fiber diameter is controlled at 8 - 12 μm.

3. The method according to claim 1, characterized in that, In the surface modification of the glass fibers, the plasma treatment uses a nitrogen atmosphere, the power is 100 - 200 W, and the treatment time is 5 - 10 minutes; the silane coupling agent is γ-aminopropyltriethoxysilane, and the coating thickness is 50 - 100 nm.

4. The method according to claim 1, wherein The deposition of the graphene oxide nano-layer adopts a chemical vapor deposition process, the deposition temperature is 150 - 200 °C, and the deposition time is 30 - 60 minutes.

5. The method according to claim 1, wherein The glass transition temperature of the polyimide resin is not lower than 350 °C, and the thermal decomposition temperature is not lower than 500 °C.

6. The method according to claim 1, wherein In the modified resin matrix, the diameter of the multi-walled carbon nanotubes is 10 - 20 nm, and the length is 5 - 15 μm; the particle size of the nano-SiO2 particles is 20 - 50 nm.

7. The method according to claim 1, characterized in that, In the resin transfer molding process, the volume fraction of the glass fibers is controlled at 55 - 65%, and the resin injection speed is 50 - 100 mL / min.

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