Surface treatment process method for improving interface performance of electronic-grade glass fiber

Abstract

The invention discloses a surface treatment process method for improving the interface performance of electronic-grade glass fibers, and belongs to the technical field of surface modification of the electronic-grade glass fibers. The specific process comprises the following steps: firstly, pretreating electronic-grade glass fiber cloth with acetone to remove impurities; then, forming a PDA coating on the surface through self-polymerization reaction of dopamine, capturing Zn < 2 + > and providing reaction sites by utilizing phenolic hydroxyl groups and amido groups of PDA; after ZnO seed synthesis and annealing treatment, inducing ZnO nanorods to uniformly grow in a mixed solution containing PEI; according to the method, the electronic-grade glass fiber cloth is synergistically modified through PDA, ZnO and PEI, and a nucleation induction-structure stabilization-interface reaction integrated interface enhancement mechanism is constructed, so that the problem of insufficient interface bonding force between the glass fiber and epoxy resin is solved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of surface modification of electronic-grade glass fibers, and particularly relates to a surface treatment process method for improving the interface performance of electronic-grade glass fibers. BACKGROUND

[0002] Electronic-grade glass fibers are inorganic non-metallic materials with silicate as the main component, which have good insulation performance, high-temperature resistance and chemical corrosion resistance. The inside of the electronic-grade glass fibers is composed of slender glass filaments, and the surface is smooth, with high mechanical strength, light weight and low price. The electronic-grade glass fibers are one of the most widely used reinforcing materials at present. The electronic-grade glass fibers can be combined with unsaturated polyester resin, epoxy resin, phenolic resin and other high molecular materials to form glass fiber composite materials with excellent performance, good strength-to-weight ratio, processing formability and dimensional stability, and are widely used in integrated circuits, electrical materials, wind power and other fields.

[0003] During the preparation process of glass fibers by melt drawing, the glass fibers need to undergo high-temperature rapid cooling, and finally form an amorphous structure with high orientation, that is, the glass fibers are arranged in order on a macro scale, but there is no long-range ordered microstructure inside the glass fibers on a micro scale, and the molecules are arranged randomly. The surface of the glass fibers is dense, the content of active functional groups is low, and the chemical inertness is strong. This characteristic leads to low adhesion between the glass fiber and the resin interface, and the composite material is prone to interlaminar delamination, peeling and other failure phenomena, which seriously affects the mechanical properties and service life of the composite material in the actual application and production process. Therefore, before the glass fibers are used to reinforce the composite material, the surface of the glass fibers needs to be functionalized and modified to increase the roughness of the glass fiber surface and introduce active groups, so as to improve the interfacial adhesion between the glass fiber and the resin matrix.

[0004] Polydopamine (PDA) is a kind of biomimetic coating material which simulates the structure of dopamine in the byssal threads of mussels. It can self-assemble and deposit on the surface of various materials under mild conditions to form a uniform functional film layer. Its surface is rich in various active functional groups (such as phenolic hydroxyl, amine group, etc.), which can significantly improve the surface chemical activity of glass fibers and provide excellent interfacial bonding sites. At the same time, zinc oxide (ZnO) nanoparticles, as an inorganic material with good stability and excellent antibacterial and ultraviolet resistance, can be uniformly loaded on the surface of glass fibers through the reduction deposition of the PDA layer, not only enhancing the mechanical interlocking effect between the interfaces, but also endowing the material with certain functionality. The synergistic modification of PDA and ZnO on electronic-grade glass fiber cloth can significantly improve the bonding performance between the glass fiber and the epoxy resin matrix, thereby improving the overall mechanical properties and environmental adaptability of the composite material. However, although the PDA+ZnO synergistic modification system can enhance the interfacial adhesion between glass fibers and epoxy resin to some extent, it still has certain limitations: first, the attachment of ZnO is highly dependent on the reaction sites provided by the PDA surface. Due to the uniform distribution of functional groups on the surface of the PDA film, the deposition of ZnO on the surface of the glass fiber is prone to aggregation or size inconsistency, affecting the stability and consistency of the interfacial reinforcement structure; second, the PDA layer alone in an alkaline environment is prone to hydrolysis and peeling, which can lead to problems such as ZnO falling off and interfacial adhesion decreasing under long-term service conditions; at the same time, PDA and epoxy resin mainly rely on physical interactions such as hydrogen bonding and van der Waals forces, lacking stable chemical bonding, which cannot achieve true interfacial synergistic reinforcement. Therefore, the single PDA+ZnO system cannot meet the application requirements of high-performance interfacial reinforcement, and there is room for further optimization. SUMMARY

[0005] To solve the above technical problems, the present application provides a surface treatment process for improving the interfacial performance of electronic-grade glass fibers.

[0006] To achieve the above-mentioned purpose, the present application provides the following technical solution: a surface treatment process for improving the interfacial performance of electronic-grade glass fibers, which modifies the electronic-grade glass fiber cloth to improve the interfacial bonding performance between the glass fiber and the epoxy resin. The modification method is to treat the electronic-grade glass fiber cloth with polydopamine, zinc oxide, and polyethyleneimine, and to generate zinc oxide nanocolumns on the surface of the electronic-grade glass fiber cloth to increase the surface roughness.

[0007] Preferably, the modification method comprises the following steps:

[0008] Step 1: impurity removal treatment of the electronic-grade glass fiber cloth to obtain the original electronic-grade glass fiber cloth;

[0009] Step 2, preparing dopamine aqueous solution, the treated electronic grade glass fiber cloth in step 1 is soaked into the dopamine aqueous solution to realize polymerization of dopamine;

[0010] Step 3, zinc oxide seed synthesis: zinc acetate ethanol solution and sodium hydroxide ethanol solution are selected to be mixed in a volume ratio of 5:1, and after ice water bath cooling, the mixture is stored at room temperature for 1h, and the electronic grade glass fiber cloth in step 2 is completely soaked in the above mixed solution;

[0011] Step 4, the electronic grade glass fiber cloth after zinc oxide seed synthesis is annealed for 3 times;

[0012] Step 5, zinc nitrate hexahydrate solution and methenamine solution are mixed in a ratio of 1:2, and polyethyleneimine solution is added at the same time, and the pH value is adjusted to 6-7, and the electronic grade glass fiber cloth after annealing is soaked in the mixed solution, and the reaction is carried out in a closed environment at 90℃.

[0013] Step 6, the electronic grade glass fiber cloth in step 5 is washed and dried to obtain ZnO-PDA-PEI-GF.

[0014] Preferably, in step 1, the electronic grade glass fiber cloth is completely soaked in acetone for 24h to remove the sizing agent and impurities on the surface, and the original electronic grade glass fiber cloth is obtained after washing and drying.

[0015] Preferably, in step 2, tris buffer is added to the dopamine aqueous solution to obtain 1g / L, pH=8 hydrochloric acid dopamine aqueous solution.

[0016] Preferably, in step 3, 12.5mol / L zinc acetate ethanol solution and 20mol / L sodium hydroxide ethanol solution are prepared, and both solutions are stirred at 65℃ for 30min; the two solutions are stirred at 65℃ for 30min in a volume ratio of A:B=5:1, and after ice water bath cooling, the mixture is stored at room temperature for 1h; the electronic grade glass fiber cloth is completely soaked in the above mixed solution for 20min.

[0017] Preferably, the zinc acetate ethanol solution is prepared by stirring 1.372g of analytical pure zinc acetate and 500mL of ethanol at 65℃ for 30min; the sodium hydroxide ethanol solution is prepared by stirring 0.8g of analytical pure sodium hydroxide and 100mL of ethanol at 65℃ for 30min.

[0018] Preferably, in step 5, 0.05mol / L zinc nitrate hexahydrate solution and 0.025mol / L methenamine solution are mixed in a ratio of 1:2.

[0019] Preferably, in step 4, the electronic-grade glass fiber cloth is annealed three times at 150°C, with each annealing time being 10 minutes. In this invention, the formation process of ZnO nanopillars is treated with three annealing processes at 150°C. The purpose is to promote the dehydroxylation crystallization, preferential grain growth, and stress release of the ZnO precursor through three staged treatments, thereby obtaining a highly ordered and well-arranged ZnO nanopillar array. The step-by-step heat treatment not only improves the crystallinity and stability of ZnO, but also avoids the problems of agglomeration and PDA carbonization that may be caused by a single high-temperature annealing. The repeated heat treatment process can also enhance the mechanical interlocking force and interfacial bonding performance between ZnO and the PDA / PEI composite substrate.

[0020] Preferably, in step 5, the molar concentration of the polyethyleneimine solution is 1-3 mMol, preferably 3 mMol, and the polyethyleneimine solution is prepared by mixing analytical grade and distilled water.

[0021] Preferably, in step 6, the electronic-grade glass fiber cloth is ultrasonically cleaned for 20 minutes and dried at 100°C for 2 hours.

[0022] This invention also proposes a modified electronic-grade glass fiber reinforced epoxy resin matrix composite material, which is formed by combining electronic-grade glass fiber modified by the above-mentioned method with epoxy resin through vacuum infusion. SEM images were used to observe the interface between glass fiber and epoxy resin, and it was found that the modified interface has a stronger adhesion and the interlaminar shear strength can reach up to 77.94 MPa, which is up to 36.4% higher than that of the unmodified electronic-grade glass fiber reinforced epoxy resin matrix composite material.

[0023] Compared with the prior art, the present invention provides a surface treatment process for improving the interface properties of electronic-grade glass fibers, which has the following beneficial effects:

[0024] (1) This invention improves the interfacial bonding performance between electronic-grade glass fiber cloth and epoxy resin by modifying the cloth. Specifically, the modification involves polydopamine (PDA) + zinc oxide (ZnO) + polyethyleneimine (PEI) + electronic-grade glass fiber cloth, increasing surface roughness by generating zinc oxide nanopillars on the surface of the glass fiber cloth. PDA can form an adhesive coating rich in polyphenolic hydroxyl and amine groups on the glass fiber surface through a self-polymerization reaction, which not only improves the adhesion of the fiber surface to ZnO but also enhances the bonding performance between the fiber and epoxy resin. 2 The ability to capture ZnO also provides abundant reaction sites for subsequent nucleation of ZnO. ZnO can grow in situ on the PDA coating to form nanopillar structures. These nanostructures can significantly improve the surface roughness and mechanical interlocking of glass fibers. At the same time, their polar surfaces can interact with epoxy resin through hydrogen bonding, electrostatics, and other processes, further enhancing interfacial adhesion.

[0025] (2) Based on PDA+ZnO as the modified material, this invention introduces a novel modification variable, PEI. The primary and secondary amine groups abundant in the PEI molecular chain can interact with Zn. 2 + ions undergo a complexation reaction, forming a highly uniformly distributed Zn on the glass fiber surface. 2 The addition of complexation sites induces preferential ZnO nucleation in localized areas under the alkaline conditions provided by polydopamine, preventing localized aggregation. The PEI polymer structure spreads in a brush-like pattern on the fiber surface, exhibiting a significant steric hindrance effect, effectively limiting the excessive growth and aggregation of ZnO crystal nuclei, thereby controlling the size and arrangement density of the ZnO nanostructures. After protonation, PEI exhibits a positive charge distribution, generating electrostatic repulsion during ZnO nanocrystal formation, further inhibiting particle aggregation and promoting the uniform and orderly deposition of ZnO into a nanopillar array structure on the glass fiber surface. The synergistic effect of these three factors significantly improves the interlaminar shear strength of the composite material compared to the unmodified system, solving the problems of insufficient interfacial bonding and poor stability in the traditional PDA+ZnO system. Attached Figure Description

[0026] The accompanying drawings are provided to further illustrate the invention and form part of the specification. They are used together with the embodiments of the invention to explain the invention, but do not constitute a limitation thereof. In the drawings:

[0027] Figure 1 This is a flowchart of the electronic-grade glass fiber modification process proposed in this invention.

[0028] Figure 2 This is a SEM image of unmodified electronic-grade glass fiber.

[0029] Figure 3 This is a SEM image of the modified glass fiber prepared in Example 1.

[0030] Figure 4 This is a SEM image of the modified glass fiber prepared in Example 2.

[0031] Figure 5 This is a SEM image of the modified glass fiber prepared in Example 3.

[0032] Figure 6 This is a SEM image of an unmodified glass fiber composite material in the prior art.

[0033] Figure 7 This is a SEM image of the modified glass fiber composite material of the present invention.

[0034] Figure 8 This is a schematic diagram of the modified electronic-grade glass fiber cloth of the present invention. 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. The components of the embodiments of the present invention described and shown in the accompanying drawings can generally be arranged and designed in various different configurations. Therefore, the following detailed description of the embodiments of the present invention provided in the accompanying drawings is not intended to limit the scope of the claimed invention, but merely to illustrate selected embodiments of the invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

[0036] Example 1

[0037] This embodiment proposes a surface treatment process to improve the interfacial properties of electronic-grade glass fiber. The process involves modifying the electronic-grade glass fiber cloth to enhance its interfacial bonding with epoxy resin. The modification method involves treating the electronic-grade glass fiber cloth with polydopamine (PDA), zinc oxide (ZnO), and polyethyleneimine (PEI), thereby generating zinc oxide nanopillars on the surface of the electronic-grade glass fiber cloth to improve surface roughness. The specific modification steps are as follows:

[0038] S1. Immerse the electronic-grade glass fiber cloth completely in acetone for 24 hours to remove the sizing agent and impurities on the surface. After cleaning and drying, the original electronic-grade glass fiber cloth is obtained.

[0039] S2. Add triaminomethane buffer (Tris) to the dopamine aqueous solution to obtain a 1 g / L dopamine hydrochloride aqueous solution with pH=8.

[0040] S3. Immerse the electronic-grade glass fiber cloth in the solution in S2 for 24 hours to achieve the polymerization of dopamine on the electronic-grade glass fiber.

[0041] S4. Prepare a 12.5 mol / L zinc acetate ethanol solution (solution A) and a 20 mol / L sodium hydroxide ethanol solution (solution B). Both solutions were stirred at 65°C for 30 min. The two solutions were then stirred at 65°C for 30 min at a volume ratio of A:B = 5:1, cooled in an ice-water bath, and stored at room temperature for 1 h. Solution A was prepared by stirring 1.372 g of analytical grade zinc acetate with 500 mL of ethanol at 65°C for 30 min, and solution B was prepared by stirring 0.8 g of analytical grade sodium hydroxide with 100 mL of ethanol at 65°C for 30 min.

[0042] S5. Completely immerse the electronic-grade glass fiber cloth from S3 in the mixed solution from step S4 for 15 minutes to ensure uniform synthesis of ZnO seeds.

[0043] S6. The electronic-grade glass fiber cloth soaked in step S5 is annealed three times at 150°C, with each annealing time being 10 minutes.

[0044] S7. Mix 0.05 mol / L zinc nitrate hexahydrate solution and 0.025 mol / L hexamethylenetetramine solution at a ratio of 1:2, and simultaneously add 1 mmol polyethyleneimine solution (PEI). Adjust the pH to 6-7, and stir at room temperature for 30 min to ensure complete dissolution. The 1 mmol polyethyleneimine solution (PEI) is prepared by mixing 0.09 g of analytical grade polyethyleneimine with 50 mL of distilled water.

[0045] S8. Immerse the electronic-grade glass fiber cloth obtained in step S6 in the mixed solution of step S7, and seal the reaction at 90°C for 4 hours.

[0046] S9. Take out the modified electronic-grade glass fiber cloth from step S8, ultrasonically clean it for 10 minutes, and dry it at 100℃ for 2 hours to finally obtain ZnO-PDA-PEI-GF.

[0047] This embodiment also proposes a modified electronic-grade glass fiber reinforced epoxy resin matrix composite material, which is formed by vacuum infusion and consists of five layers of modified electronic-grade glass fiber combined with epoxy resin.

[0048] The interface between glass fiber and epoxy resin was observed using SEM images. The interlaminar shear strength of the modified electronic-grade glass fiber reinforced epoxy resin matrix composite was 60.83 MPa, which was 6.5% higher than that of the unmodified electronic-grade glass fiber reinforced epoxy resin matrix composite.

[0049] Example 2

[0050] This embodiment proposes a surface treatment process to improve the interfacial properties of electronic-grade glass fiber. The process involves modifying the electronic-grade glass fiber cloth to enhance its interfacial bonding with epoxy resin. The modification method involves treating the electronic-grade glass fiber cloth with polydopamine (PDA), zinc oxide (ZnO), and polyethyleneimine (PEI), thereby generating zinc oxide nanopillars on the surface of the electronic-grade glass fiber cloth to improve surface roughness. The specific modification steps are as follows:

[0051] S1. Immerse the electronic-grade glass fiber cloth completely in acetone for 24 hours to remove the sizing agent and impurities on the surface. After cleaning and drying, the original electronic-grade glass fiber cloth is obtained.

[0052] S2. Add triaminomethane buffer (Tris) to the dopamine aqueous solution to obtain a 1 g / L dopamine hydrochloride aqueous solution with pH=8.

[0053] S3. Immerse the electronic-grade glass fiber cloth in the solution in S2 for 24 hours to achieve the polymerization of dopamine on the electronic-grade glass fiber.

[0054] S4. Prepare a 12.5 mol / L zinc acetate ethanol solution (solution A) and a 20 mol / L sodium hydroxide ethanol solution (solution B). Both solutions were stirred at 65°C for 30 min. The two solutions were then stirred at 65°C for 30 min at a volume ratio of A:B = 5:1, cooled in an ice-water bath, and stored at room temperature for 1 h. Solution A was prepared by stirring 1.372 g of analytical grade zinc acetate with 500 mL of ethanol at 65°C for 30 min, and solution B was prepared by stirring 0.8 g of analytical grade sodium hydroxide with 100 mL of ethanol at 65°C for 30 min.

[0055] S5. Completely immerse the electronic-grade glass fiber cloth from S3 in the mixed solution from step S4 for 15 minutes to ensure uniform synthesis of ZnO seeds.

[0056] S6. The electronic-grade glass fiber cloth soaked in step S5 is annealed three times at 150°C, with each annealing time being 10 minutes.

[0057] S7. Mix 0.05 mol / L zinc nitrate hexahydrate solution and 0.025 mol / L hexamethylenetetramine solution at a ratio of 1:2, and simultaneously add 2 mmol / L polyethyleneimine solution (PEI). Adjust the pH to 6-7, and stir at room temperature for 30 minutes to ensure complete dissolution. The 2 mmol / L polyethyleneimine solution (PEI) is prepared by mixing 0.18 g of analytical grade polyethyleneimine with 50 mL of distilled water.

[0058] S8. Immerse the electronic-grade glass fiber cloth obtained in step S6 in the mixed solution of step S7, and seal the reaction at 90°C for 4 hours.

[0059] S9. Take out the modified electronic-grade glass fiber cloth from step S8, ultrasonically clean it for 10 minutes, and dry it at 100℃ for 2 hours to finally obtain ZnO-PDA-PEI-GF.

[0060] This embodiment also proposes a modified electronic-grade glass fiber reinforced epoxy resin matrix composite material, which is formed by vacuum infusion and consists of five layers of modified electronic-grade glass fiber combined with epoxy resin.

[0061] The interface between glass fiber and epoxy resin was observed using SEM images. The interlaminar shear strength of the modified electronic-grade glass fiber reinforced epoxy resin matrix composite was 68.1 MPa, which was 19% higher than that of the unmodified electronic-grade glass fiber reinforced epoxy resin matrix composite.

[0062] Example 3

[0063] This embodiment proposes a surface treatment process to improve the interfacial properties of electronic-grade glass fiber. The process involves modifying the electronic-grade glass fiber cloth to enhance its interfacial bonding with epoxy resin. The modification method involves treating the electronic-grade glass fiber cloth with polydopamine (PDA), zinc oxide (ZnO), and polyethyleneimine (PEI), thereby generating zinc oxide nanopillars on the surface of the electronic-grade glass fiber cloth to improve surface roughness. The specific modification steps are as follows:

[0064] S1. Immerse the electronic-grade glass fiber cloth completely in acetone for 24 hours to remove the sizing agent and impurities on the surface. After cleaning and drying, the original electronic-grade glass fiber cloth is obtained.

[0065] S2. Add triaminomethane buffer (Tris) to the dopamine aqueous solution to obtain a 1 g / L dopamine hydrochloride aqueous solution with pH=8.

[0066] S3. Immerse the electronic-grade glass fiber cloth in the solution in S2 for 24 hours to achieve the polymerization of dopamine on the electronic-grade glass fiber.

[0067] S4. Prepare a 12.5 mol / L zinc acetate ethanol solution (solution A) and a 20 mol / L sodium hydroxide ethanol solution (solution B). Both solutions were stirred at 65°C for 30 min. The two solutions were then stirred at 65°C for 30 min at a volume ratio of A:B = 5:1, cooled in an ice-water bath, and stored at room temperature for 1 h. Solution A was prepared by stirring 1.372 g of analytical grade zinc acetate with 500 mL of ethanol at 65°C for 30 min, and solution B was prepared by stirring 0.8 g of analytical grade sodium hydroxide with 100 mL of ethanol at 65°C for 30 min.

[0068] S5. Completely immerse the electronic-grade glass fiber cloth from S3 in the mixed solution from step S4 for 15 minutes to ensure uniform synthesis of ZnO seeds.

[0069] S6. The electronic-grade glass fiber cloth soaked in step S5 is annealed three times at 150°C, with each annealing time being 10 minutes.

[0070] S7. Mix 0.05 mol / L zinc nitrate hexahydrate solution and 0.025 mol / L hexamethylenetetramine solution in a 1:2 ratio, and simultaneously add 3 mmol / L polyethyleneimine solution (PEI). Adjust the pH to 6-7, and stir at room temperature for 30 min to ensure complete dissolution. The 3 mmol / L polyethyleneimine solution (PEI) is prepared by mixing 0.27 g of analytical grade polyethyleneimine with 50 mL of distilled water.

[0071] S8. Immerse the electronic-grade glass fiber cloth obtained in step S6 in the mixed solution of step S7, and seal the reaction at 90°C for 4 hours.

[0072] S9. Take out the modified electronic-grade glass fiber cloth from step S8, ultrasonically clean it for 10 minutes, and dry it at 100℃ for 2 hours to finally obtain ZnO-PDA-PEI-GF.

[0073] This embodiment also proposes a modified electronic-grade glass fiber reinforced epoxy resin matrix composite material, which is formed by vacuum infusion and consists of five layers of modified electronic-grade glass fiber combined with epoxy resin.

[0074] The interface between glass fiber and epoxy resin was observed using SEM images. The interlaminar shear strength of the modified electronic-grade glass fiber reinforced epoxy resin matrix composite was 77.94 MPa, which was 36.4% higher than that of the unmodified electronic-grade glass fiber reinforced epoxy resin matrix composite.

[0075] Comparative Example 1

[0076] This embodiment proposes a surface treatment process to improve the interfacial properties of electronic-grade glass fiber. The process involves modifying the electronic-grade glass fiber cloth to enhance its interfacial bonding with epoxy resin. The modification method involves treating the electronic-grade glass fiber cloth with polydopamine (PDA) and zinc oxide (ZnO), thereby generating zinc oxide nanopillars on the surface of the electronic-grade glass fiber cloth to improve surface roughness. The specific modification steps are as follows:

[0077] S1. Immerse the electronic-grade glass fiber cloth completely in acetone for 24 hours to remove the sizing agent and impurities on the surface. After cleaning and drying, the original electronic-grade glass fiber cloth is obtained.

[0078] S2. Add triaminomethane buffer (Tris) to the dopamine aqueous solution to obtain a 1 g / L dopamine hydrochloride aqueous solution with pH=8.

[0079] S3. Immerse the electronic-grade glass fiber cloth in the solution in S2 for 24 hours to achieve the polymerization of dopamine on the electronic-grade glass fiber.

[0080] S4. Prepare a 12.5 mol / L zinc acetate ethanol solution (solution A) and a 20 mol / L sodium hydroxide ethanol solution (solution B). Both solutions were stirred at 65°C for 30 min. The two solutions were then stirred at 65°C for 30 min at a volume ratio of A:B = 5:1, cooled in an ice-water bath, and stored at room temperature for 1 h. Solution A was prepared by stirring 1.372 g of analytical grade zinc acetate with 500 mL of ethanol at 65°C for 30 min, and solution B was prepared by stirring 0.8 g of analytical grade sodium hydroxide with 100 mL of ethanol at 65°C for 30 min.

[0081] S5. Completely immerse the electronic-grade glass fiber cloth from S3 in the mixed solution from step S4 for 15 minutes to ensure uniform synthesis of ZnO seeds.

[0082] S6. The electronic-grade glass fiber cloth soaked in step S5 is annealed three times at 150°C, with each annealing time being 10 minutes.

[0083] S7. Mix 0.05 mol / L zinc nitrate hexahydrate solution and 0.025 mol / L hexamethylenetetramine solution in a 1:2 ratio and stir at room temperature for 30 minutes to ensure complete dissolution.

[0084] S8. Immerse the electronic-grade glass fiber cloth obtained in step S6 in the mixed solution of step S7, and seal the reaction at 90°C for 4 hours.

[0085] S9. Take out the modified electronic-grade glass fiber cloth from step S8, ultrasonically clean it for 10 minutes, and dry it at 100℃ for 2 hours to finally obtain ZnO-PDA-GFRP.

[0086] This embodiment also proposes a modified electronic-grade glass fiber reinforced epoxy resin matrix composite material, which is formed by vacuum infusion and consists of five layers of modified electronic-grade glass fiber combined with epoxy resin.

[0087] SEM images were used to observe the interface between glass fiber and epoxy resin. The interlaminar shear strength was 59.41 MPa, which was 4% higher than that of the unmodified electronic-grade glass fiber reinforced epoxy resin matrix composite.

[0088] Comparative Example 2

[0089] The electronic-grade glass fiber reinforced epoxy resin matrix composite material proposed in this embodiment is composed of five layers of unmodified electronic-grade glass fiber cloth bonded with epoxy resin. Following GB / T30969-2014, shear specimens measuring 3cm in length, 2.5cm in width, and 4mm in thickness were prepared. The interlaminar shear strength of the final electronic-grade glass fiber reinforced epoxy resin matrix composite material is approximately 57.125 MPa.

[0090] Figure 3 —5 shows the formation of zinc oxide nanopillars on glass fibers with different concentrations of PEI in three embodiments of the present invention. It can be observed that the zinc oxide nanopillars formed after the addition of 3 mol PEI are more uniform and abundant than those formed by the other two methods.

[0091] Figure 6 and Figure 7 The images show SEM cross-sectional views of unmodified and modified glass fiber epoxy resin composites, respectively. The cylindrical shapes represent glass fibers. Figure 6 There is almost no epoxy resin adhering to the fiber, while Figure 7 The surface of the glass fiber has many agglomerates, indicating that the interfacial bonding performance has been improved after modification.

[0092] In the description of this invention, the terms "first," "second," "another," and "yet another" are used for descriptive purposes only and should not be construed as indicating or implying relative importance or implicitly specifying the number of indicated technical features. Thus, features defined as "first" or "second" may explicitly or implicitly include one or more features. In the description of embodiments of this invention, "a plurality of" means two or more, unless otherwise explicitly specified.

[0093] In the description of this invention, it should be noted that, unless otherwise explicitly specified and limited, the terms "connected" and "linked" should be interpreted broadly. For example, they can refer to a fixed connection, a detachable connection, or an integral connection; they can refer to a mechanical connection or an electrical connection; they can refer to a direct connection or an indirect connection through an intermediate medium. Those skilled in the art can understand the specific meaning of the above terms in this invention based on the specific circumstances. Furthermore, in the description of this invention, unless otherwise stated, "a plurality of" means two or more.

[0094] Although embodiments of the invention have been shown and described, those skilled in the art will understand that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents.

Claims

1. A surface treatment process for improving the interfacial properties of electronic-grade glass fiber, characterized by modifying the electronic-grade glass fiber cloth to improve its interfacial bonding performance with epoxy resin, wherein... The modification method involves treating electronic-grade glass fiber cloth with polydopamine, zinc oxide, and polyethyleneimine, thereby increasing the surface roughness by generating zinc oxide nanopillars on the surface of the electronic-grade glass fiber cloth.

2. The surface treatment process for improving the interfacial properties of electronic-grade glass fiber according to claim 1, characterized in that, The modification method includes the following steps: Step 1: Remove impurities from the electronic-grade glass fiber cloth to obtain the original electronic-grade glass fiber cloth; Step 2: Prepare a dopamine aqueous solution by immersing the electronic-grade glass fiber cloth treated in Step 1 into the dopamine aqueous solution to achieve dopamine polymerization. Step 3, Zinc oxide seed synthesis: Select zinc acetate ethanol solution and sodium hydroxide ethanol solution and mix them in a volume ratio of 5:

1. After cooling in an ice water bath, store at room temperature for 1 hour. Completely immerse the electronic grade glass fiber cloth from step 2 in the above mixed solution. Step 4: The electronic-grade glass fiber cloth synthesized from zinc oxide seeds undergoes three annealing treatments. Step 5: Mix zinc nitrate hexahydrate solution and hexamethylenetetramine solution in a 1:2 ratio, add polyethyleneimine solution at the same time, adjust the pH value to 6-7, immerse the annealed electronic grade glass fiber cloth in the mixed solution, and seal the reaction at 90°C. Step 6: Clean and dry the electronic-grade glass fiber cloth from Step 5 to finally obtain ZnO-PDA-PEI-GF.

3. The surface treatment process for improving the interfacial properties of electronic-grade glass fiber according to claim 2, characterized in that, In step 1, the electronic-grade glass fiber cloth is completely immersed in acetone for 24 hours to remove the sizing agent and impurities on the surface. After cleaning and drying, the original electronic-grade glass fiber cloth is obtained.

4. The surface treatment process for improving the interfacial properties of electronic-grade glass fiber according to claim 2, characterized in that, In step 2, triaminomethane buffer is added to the dopamine aqueous solution to obtain a 1 g / L dopamine hydrochloride aqueous solution with pH=8.

5. The surface treatment process for improving the interfacial properties of electronic-grade glass fiber according to claim 2, characterized in that, In step 3, a 12.5 mol / L zinc acetate ethanol solution and a 20 mol / L sodium hydroxide ethanol solution were prepared. Both solutions were stirred at 65 °C for 30 min. The two solutions were then stirred at 65 °C for 30 min at a volume ratio of A:B = 5:

1. After cooling in an ice-water bath, the solutions were stored at room temperature for 1 h. The electronic-grade glass fiber cloth was completely immersed in the above mixed solution for 20 minutes.

6. The surface treatment process for improving the interfacial properties of electronic-grade glass fiber according to claim 5, characterized in that, The zinc acetate ethanol solution was prepared by stirring 1.372 g of analytical grade zinc acetate with 500 mL of ethanol at 65 °C for 30 min; the sodium hydroxide ethanol solution was prepared by stirring 0.8 g of analytical grade sodium hydroxide with 100 mL of ethanol at 65 °C for 30 min.

7. The surface treatment process for improving the interfacial properties of electronic-grade glass fiber according to claim 2, characterized in that, In step 5, a 0.05 mol / L zinc nitrate hexahydrate solution and a 0.025 mol / L hexamethylenetetramine solution are mixed in a 1:2 ratio.

8. The surface treatment process for improving the interfacial properties of electronic-grade glass fiber according to claim 2, characterized in that, In step 4, the electronic-grade glass fiber cloth is annealed three times at 150°C, with each annealing time being 10 minutes.

9. A surface treatment process for improving the interfacial properties of electronic-grade glass fibers according to claim 2 or 7, characterized in that, In step 5, the molar concentration of the polyethyleneimine solution is 1–3 mmol, and the polyethyleneimine solution is prepared by mixing analytical grade and distilled water.

10. The preparation method of the surface treatment process for improving the interfacial properties of electronic-grade glass fiber according to claim 2, characterized in that, In step 6, the electronic-grade glass fiber cloth is ultrasonically cleaned for 20 minutes and dried at 100°C for 2 hours.

11. A modified electronic-grade glass fiber reinforced epoxy resin matrix composite material, characterized in that, It is made by vacuum infusion of electronic-grade glass fiber modified by any one of claims 1-10 and epoxy resin.

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