Glass fabric and preparation method thereof

Abstract

The invention relates to the technical field of glass fiber materials, in particular to glass fiber cloth and a preparation method thereof. Through multi-angle technical improvement of base material component innovation, composite modifier design and preparation parameter synergy, the glass fabric with high strength, high elasticity and strong oxidation resistance is prepared, the requirements of aerospace, high-end electronics and other fields with strict requirements for material performance can be met, and remarkable technical value and market potential are achieved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of glass fiber materials, in particular to a glass fiber cloth and a preparation method thereof. BACKGROUND

[0002] The glass fiber cloth is widely used in the fields of electronics, building materials, aerospace, etc. due to its light weight, high strength, corrosion resistance, etc. However, there are two problems in the actual production of the glass fiber cloth: first, the strong elasticity is insufficient, and the conventional glass fiber is based on a system of SiO2, Al2O3 and CaO, and Ca 2+ The damage to the glass network leads to brittle fracture of the fiber, and the elongation at break is generally less than 3%; second, the oxidation resistance is poor, and the hydroxyl group on the surface of the glass fiber is easy to react with oxygen to generate cracks, resulting in attenuation of mechanical properties, and the tensile strength retention rate is usually less than 70% after 1000h of thermal oxidation aging at 150℃.

[0003] The existing technical improvement methods for this problem are mostly focused on optimizing a single aspect of performance, such as adding ZrO2 to improve strength, but this will cause the melting temperature to rise and the fiber to be difficult to form; using a silane coupling agent (such as KH550) to modify the surface can improve the interfacial bonding force, but the oxidation resistance is limited, and there is a lack of comprehensive means to comprehensively solve the problem.

[0004] Therefore, it is necessary to invent a comprehensive glass fiber cloth preparation method to produce high-strength, high-elasticity and strong-oxidation-resistant glass fiber cloth. SUMMARY

[0005] In view of the above technical problems, the present application provides a glass fiber cloth and a preparation method thereof, which is prepared by multi-angle technical improvement of "substrate component innovation-composite modifier design-preparation parameter coordination", and has high strength, high elasticity and strong oxidation resistance, and can meet the needs of the fields of aerospace, high-end electronics, etc. which have strict requirements on material performance.

[0006] The present application discloses a kind of glass fiber cloth, which is composed of the following raw materials by weight fraction: Silicon dioxide 60~65 parts, aluminum oxide 15~18 parts, niobium pentoxide 3~5 parts, gallium oxide 2~4 parts, cerium oxide 1~3 parts, lithium oxide 0.5~1.5 parts, zirconium oxide 1~2 parts, composite modifier 1.2~2 parts.

[0007] Preferably, the composite modifier is composed of modified PEA and nano-titanium dioxide.

[0008] Preferably, the mass ratio of modified PEA and nano-titanium dioxide is (1.5~2.5):1.

[0009] Preferably, the modified PEA is a grafting of KH550 silane on PEA to form an amino-terminated polyetheramine grafted gamma-aminopropyl triethoxysilane.

[0010] The application also discloses a preparation method of the glass fabric. S1 base material melting: silica, alumina, niobium pentoxide, gallium oxide, cerium oxide, lithium oxide, zirconium oxide are mixed in proportion, put into a melting furnace, melted at 1580-1620 DEG C, and kept for 2.5-3.5 h to obtain a uniform glass melt; S2 wire drawing forming: the glass melt obtained in the step S1 is introduced into a wire drawing machine die plate, and is drawn at 1280-1320 DEG C to obtain glass monofilament with a diameter of 8-12 microns; S3 surface modification: a modifier solution is prepared by dissolving a composite modifier in a mixed solvent of ethanol and water, and then ultrasonic dispersion is performed; the glass monofilament prepared in the step S2 is immersed in the modifier solution, soaked at 45-55 DEG C for 15-25 min, and then taken out and solidified at 120-140 DEG C for 1.5-2.5 h to obtain modified glass monofilament; S4 weaving forming: the modified glass monofilament obtained in the step S3 is woven by warp and weft, and a rapier loom is used, the warp and weft density is 28-32 roots / cm, and the weaving speed is 180-220 r / min to obtain the glass fabric.

[0011] Preferably, in the step S1 base material melting, the heating rate of the melting furnace is 5-8 DEG C / min.

[0012] Preferably, in the step S2 wire drawing forming, the drawing speed of the wire drawing machine is 850-950 m / min.

[0013] Preferably, in the step S3 surface modification, the volume ratio of the ethanol and water is 8:2, and the mass fraction of the modifier solution is 5-8%.

[0014] Preferably, in the step S3 surface modification, the power of the ultrasonic dispersion is 300-400 W.

[0015] Preferably, in the step S3 surface modification, the time of the ultrasonic dispersion is 20-30 min.

[0016] Compared with the prior art, the application has the beneficial effects that: The application provides a glass fabric with high strength, high elasticity and strong oxidation resistance and a preparation method thereof. The glass fabric with high strength, high elasticity and strong oxidation resistance is prepared through multi-angle technical improvement of "base material component innovation-composite modifier design-preparation parameter coordination", and the specific method is as follows. (1) Base material of niobium pentoxide and gallium oxide synergistically regulate glass network structure, Nb 3+ Embedded network enhances compactness, Ga 3+ Weak crosslinking improves flexibility, and the long-chain polyether elastic buffer layer of modifier PEA makes the tensile strength of glass cloth reach 800-850MPa, which is 17-25% higher than that of commercially available glass cloth (650-700MPa); the elongation at break reaches 3.6-4.0%, which is 25-75% higher than that of conventional glass cloth (2.0-2.8%).

[0017] (2) Ce 4+ / Ce 3+ of base material cerium oxide forms a "double antioxidant center" with modified nano-titanium dioxide, and cerium oxide captures oxidizing free radicals, titanium dioxide absorbs ultraviolet light and inhibits electron-hole recombination, and cooperatively resists thermal oxidative aging. After 1000h of thermal oxidative aging at 150℃, the tensile strength retention rate of the glass cloth reaches 90-94%, which is more than 20% higher than that of the prior art (≤70%); the retention rate after 1000h of ultraviolet aging is still 88%, solving the problem of rapid performance degradation in high temperature or outdoor scenarios.

[0018] (3) In the composite modifier, KH550 is combined with the hydroxyl group on the surface of the glass fiber through chemical bonds, and is fully cured at 120-140℃, so that the adhesion of the modified layer is excellent, and the strength attenuation rate after multiple water washing is only 2.8-4.5%, which is much lower than that of pure KH550 modification (8.0%) and commercially available products (10.5%); after being placed in a high-humidity environment of 85℃ and 85% for 1000h, the strength retention rate reaches 85%, effectively blocking the invasion of water vapor and corrosive substances, and adapting to complex application scenarios such as humidity and multiple water washing.

[0019] (4) The base material of lithium oxide reduces the melting temperature to 1580-1620℃, avoiding the difficulty of melting high-melting-point components; the drawing temperature and drawing speed are precisely matched, taking into account performance and cost, providing protection for industrialization.

[0020] In summary, the glass cloth of the present patent has excellent comprehensive performance, can meet the needs of the fields such as aerospace and high-end electronics which have strict requirements on material performance, and has significant technical value and market potential. DETAILED DESCRIPTION

[0021] The following examples are provided to better further understand the present application, and do not limit the content and protection scope of the present application. Any person who obtains any product the same as or similar to the present application under the inspiration of the present application or by combining the present application with other prior art features falls within the protection scope of the present application.

[0022] The specific experimental steps or conditions are not specified in the examples, and the conventional experimental steps described in the literature in the art can be performed. The reagents or instruments used are not specified by the manufacturer, and are conventional reagent products that can be obtained commercially.

[0023] Example 1: A glass fiber cloth consists of the following ingredients by weight: Silicon dioxide 62 parts, aluminum oxide 16 parts, niobium pentoxide 4 parts, gallium oxide 3 parts, cerium oxide 2 parts, lithium oxide 1 part, zirconium oxide 1.5 parts, composite modifier 1.6 parts. Among them, the modified PEA is grafted with KH550 silane to form an amino-terminated polyether amine grafted with γ-aminopropyl triethoxysilane; the composite modifier is composed of modified PEA and nano titanium dioxide in a mass ratio of 1.85:1.

[0024] A method for preparing a glass fiber cloth, comprising the following steps: S1 substrate melting: mix silicon dioxide, aluminum oxide, niobium pentoxide, gallium oxide, cerium oxide, lithium oxide, and zirconium oxide in proportion, and put them into a melting furnace. The heating rate of the melting furnace is 6.5℃ / min, and the melting is carried out at 1600℃ for 3h to obtain a uniform glass melt; S2: drawing forming: introduce the glass melt obtained in step S1 into the drawing machine casting board, and draw at 1300℃. The drawing speed of the drawing machine is 900m / min, and the diameter of the glass fiber monofilament is 10μm; S3: surface modification: dissolve the composite modifier in a mixed solvent of ethanol and water, and the volume ratio of ethanol to water is 8:2; prepare a modifier solution with a mass fraction of 6.5%, and then perform ultrasonic dispersion. The power of ultrasonic dispersion is 360W, and the time of ultrasonic dispersion is 26min; immerse the glass fiber monofilament prepared in step S2 in the modifier solution, and soak at 50℃ for 20min; take out the glass fiber monofilament, and solidify at 130℃ for 2h to obtain modified glass fiber monofilament; S4: weaving forming: weave the modified glass fiber monofilament obtained in step S3 by warp and weft, using a rapier loom, with a warp and weft density of 30 roots / cm and a weaving speed of 200r / min to obtain a glass fiber cloth.

[0025] Example 2: A glass fiber cloth consists of the following ingredients by weight: Silicon dioxide 60 parts, aluminum oxide 18 parts, niobium pentoxide 5 parts, gallium oxide 2 parts, cerium oxide 1 part, lithium oxide 1.5 parts, zirconium oxide 1 part, composite modifier 2 parts. Among them, the modified PEA is grafted with KH550 silane to form an amino-terminated polyether amine grafted with γ-aminopropyl triethoxysilane; the composite modifier is composed of modified PEA and nano titanium dioxide in a mass ratio of 2.3:1.

[0026] A method for preparing a glass fiber cloth, comprising the following steps: S1 substrate melting: silica, alumina, niobium pentoxide, gallium oxide, cerium oxide, lithium oxide, zirconium oxide are mixed in proportion, put into a melting furnace, the heating rate of the melting furnace is 5℃ / min, melted at 1620℃, and kept for 3.5h to obtain a uniform glass melt; S2 fiber forming: the glass melt obtained in step S1 is introduced into the casting wheel of the fiber drawing machine, and the glass melt is drawn at 1320℃, the drawing speed of the fiber drawing machine is 950m / min, and the diameter of the glass fiber is 8μm; S3 surface modification: the composite modifier is dissolved in a mixed solvent of ethanol and water, the volume ratio of ethanol to water is 8:2; a 5% mass fraction of the modifier solution is prepared, and then ultrasonic dispersion is carried out, the power of ultrasonic dispersion is 320W, and the time of ultrasonic dispersion is 22min; the glass fiber prepared in step S2 is immersed in the modifier solution, and soaked at 55℃ for 25min; the glass fiber is taken out and solidified at 140℃ for 2.5h to obtain modified glass fiber; S4 weaving: the modified glass fiber obtained in step S3 is woven into a glass fiber cloth by using a rapier loom, the warp and weft density is 32root / cm, and the weaving speed is 220r / min.

[0027] Example 3: a glass fiber cloth, which is composed of the following ingredients by weight: silica 65 parts, alumina 15 parts, niobium pentoxide 3 parts, gallium oxide 4 parts, cerium oxide 3 parts, lithium oxide 0.5 parts, zirconium oxide 2 parts, and composite modifier 1.2 parts. Among them, the modified PEA is a amino-terminated polyether amine grafted with KH550 silane to form a amino-terminated polyether amine grafted with gamma-aminopropyl triethoxysilane; the composite modifier is composed of modified PEA and nano titanium dioxide in a mass ratio of 1.5:1.

[0028] A method for preparing a glass fiber cloth, comprising the following steps: S1 substrate melting: silica, alumina, niobium pentoxide, gallium oxide, cerium oxide, lithium oxide, zirconium oxide are mixed in proportion, put into a melting furnace, the heating rate of the melting furnace is 5.5℃ / min, melted at 1580℃, and kept for 2.5h to obtain a uniform glass melt; S2 fiber forming: the glass melt obtained in step S1 is introduced into the casting wheel of the fiber drawing machine, and the glass melt is drawn at 1320℃, the drawing speed of the fiber drawing machine is 950m / min, and the diameter of the glass fiber is 8μm; S3 surface modification: the composite modifier is dissolved in a mixed solvent of ethanol and water, the volume ratio of ethanol and water is 8:2; a 6% by mass modifier solution is prepared, then ultrasonic dispersion is performed, the power of ultrasonic dispersion is 340W, the time of ultrasonic dispersion is 24min; the glass filament prepared in the S2 step is immersed in the modifier solution, soaked at 52℃ for 22min; the glass filament is taken out, cured at 135℃ for 2.3h, to obtain modified glass filament; S4 weaving and forming: the modified glass filament obtained in the S3 step is woven in warp and weft, a rapier loom is used, the warp and weft density is 31 roots / cm, the weaving speed is 210r / min, to obtain glass fabric.

[0029] Example 4: a glass fabric, which is composed of the following ingredients by weight: silicon dioxide 63 parts, aluminum oxide 17 parts, niobium pentoxide 4 parts, gallium oxide 3.5 parts, cerium oxide 2.5 parts, lithium oxide 1.2 parts, zirconium oxide 1.8 parts, composite modifier 1.8 parts. Among them, the modified PEA is formed by grafting KH550 silane on PEA to form an amino-terminated polyether amine grafted gamma-aminopropyl triethoxysilane; the composite modifier is composed of modified PEA and nano titanium dioxide in a mass ratio of 1.85:1.

[0030] A preparation method of a glass fabric, comprising the following steps: S1 substrate melting: silicon dioxide, aluminum oxide, niobium pentoxide, gallium oxide, cerium oxide, lithium oxide, and zirconium oxide are mixed in proportion and put into a melting furnace, the heating rate of the melting furnace is 6℃ / min, melted at 1610℃, and kept for 3.2h to obtain a uniform glass melt; S2 drawing and forming: the glass melt obtained in the S1 step is introduced into a drawing machine die plate, drawn at 1310℃, the drawing speed of the drawing machine is 920m / min, to obtain glass filaments with a diameter of 9μm; S3 surface modification: the composite modifier is dissolved in a mixed solvent of ethanol and water, the volume ratio of ethanol and water is 8:2; a 6% by mass modifier solution is prepared, then ultrasonic dispersion is performed, the power of ultrasonic dispersion is 340W, the time of ultrasonic dispersion is 24min; the glass filament prepared in the S2 step is immersed in the modifier solution, soaked at 52℃ for 22min; the glass filament is taken out, cured at 135℃ for 2.3h, to obtain modified glass filament; S4 weaving and forming: the modified glass filament obtained in the S3 step is woven in warp and weft, a rapier loom is used, the warp and weft density is 31 roots / cm, the weaving speed is 210r / min, to obtain glass fabric.

[0031] Example 5: a glass fabric, which is composed of the following ingredients by weight: Silica 64 parts, alumina 16 parts, niobium pentoxide 3.5 parts, gallium oxide 2.5 parts, cerium oxide 1.5 parts, lithium oxide 0.8 parts, zirconium oxide 1.2 parts, composite modifier 1.4 parts. Among them, the modified PEA is a gamma-aminopropyl triethoxysilane grafted with KH550 silane to form an amino-terminated polyether amine; the composite modifier is composed of modified PEA and nano titanium dioxide in a mass ratio of 2.1:1.

[0032] A method for preparing a glass fiber cloth, comprising the following steps: S1 substrate melting: mixing silica, alumina, niobium pentoxide, gallium oxide, cerium oxide, lithium oxide, and zirconium oxide in a certain proportion, and putting them into a melting furnace, the heating rate of the melting furnace is 7℃ / min, melting at 1590℃, and keeping the temperature for 2.8h to obtain a uniform glass melt; S2 wire drawing forming: introducing the glass melt obtained in step S1 into the drawing machine die plate, drawing at 1290℃, the drawing speed of the drawing machine is 880m / min, and a glass fiber single yarn with a diameter of 11μm is obtained; S3 surface modification: dissolving the composite modifier in a mixed solvent of ethanol and water, the volume ratio of ethanol to water is 8:2; preparing a modifier solution with a mass fraction of 7%, then ultrasonic dispersion, the power of ultrasonic dispersion is 380W, the time of ultrasonic dispersion is 28min; immersing the glass fiber single yarn prepared in step S2 in the modifier solution, soaking at 48℃ for 18min; taking out the glass fiber single yarn, and solidifying at 125℃ for 1.8h to obtain modified glass fiber single yarn; S4 weaving forming: weaving the modified glass fiber single yarn obtained in step S3 by warp and weft, using a rapier loom, the warp and weft density is 29root / cm, and the weaving speed is 190r / min to obtain a glass fiber cloth.

[0033] Example 6: a glass fiber cloth, which is composed of the following ingredients by weight: Silica 61 parts, alumina 17 parts, niobium pentoxide 4.5 parts, gallium oxide 3 parts, cerium oxide 2 parts, lithium oxide 1.1 parts, zirconium oxide 1.4 parts, composite modifier 1.7 parts. Among them, the modified PEA is a gamma-aminopropyl triethoxysilane grafted with KH550 silane to form an amino-terminated polyether amine; the composite modifier is composed of modified PEA and nano titanium dioxide in a mass ratio of 2.5:1.

[0034] A method for preparing a glass fiber cloth, comprising the following steps: S1 substrate melting: mixing silica, alumina, niobium pentoxide, gallium oxide, cerium oxide, lithium oxide, and zirconium oxide in a certain proportion, and putting them into a melting furnace, the heating rate of the melting furnace is 8℃ / min, melting at 1605℃, and keeping the temperature for 3.1h to obtain a uniform glass melt; S2: drawing forming: the glass melt obtained in S1 is introduced into the drawing machine's nozzle plate, and drawn at 1305℃, the drawing speed of the drawing machine is 910m / min, and a glass fiber monofilament with a diameter of 12μm is obtained; S3: surface modification: the composite modifier is dissolved in a mixed solvent of ethanol and water, the volume ratio of ethanol to water is 8:2; a modifier solution with a mass fraction of 8% is prepared, and then ultrasonic dispersion is performed, the power of ultrasonic dispersion is 400W, and the time of ultrasonic dispersion is 30min; the glass fiber monofilament prepared in S2 is immersed in the modifier solution, and soaked at 51℃ for 21min; the glass fiber monofilament is taken out and cured at 132℃ for 2.2h, and a modified glass fiber monofilament is obtained; S4: weaving forming: the modified glass fiber monofilament obtained in S3 is woven by warp and weft, a rapier loom is used, the warp and weft density is 30root / cm, and the weaving speed is 205r / min, and a glass fiber cloth is obtained.

[0035] Comparative Example 1: a glass fiber cloth is composed of the following components by weight: silicon dioxide 62 parts, aluminum oxide 16 parts, calcium oxide 7 parts, cerium oxide 2 parts, lithium oxide 1 part, zirconium oxide 1.5 parts, and composite modifier 1.6 parts. Among them, the modified PEA is a gamma-aminopropyl triethoxysilane grafted with aminoterminated polyether amine grafted with KH550 silane; the composite modifier is composed of modified PEA and nano titanium dioxide in a mass ratio of 1.85:1.

[0036] The preparation method of the glass fiber cloth is the same as that of Example 1.

[0037] Comparative Example 2: a glass fiber cloth is composed of the following components by weight: silicon dioxide 62 parts, aluminum oxide 16 parts, niobium pentoxide 4 parts, gallium oxide 3 parts, lithium oxide 1 part, zirconium oxide 1.5 parts, and composite modifier 1.6 parts. Among them, the modified PEA is a gamma-aminopropyl triethoxysilane grafted with aminoterminated polyether amine grafted with KH550 silane; the composite modifier is composed of modified PEA and nano titanium dioxide in a mass ratio of 1.85:1.

[0038] The preparation method of the glass fiber cloth is the same as that of Example 1.

[0039] Comparative Example 3: a glass fiber cloth is composed of the following components by weight: silicon dioxide 62 parts, aluminum oxide 16 parts, niobium pentoxide 4 parts, gallium oxide 3 parts, cerium oxide 2 parts, lithium oxide 1 part, zirconium oxide 1.5 parts, and KH550 silane 1.6 parts.

[0040] The preparation method of the glass fiber cloth is the same as that of Example 1.

[0041] Comparative Example 4: a glass fiber cloth is composed of the following components by weight: Silica 62 parts, alumina 16 parts, niobium pentoxide 4 parts, gallium oxide 3 parts, cerium oxide 2 parts, lithium oxide 1 part, zirconium oxide 1.5 parts, composite modifier 1.6 parts. Among them, the modified PEA is aminopropyltriethoxysilane grafted on PEA to form an amino-terminated polyether amine grafted gamma-aminopropyltriethoxysilane; the composite modifier is composed of modified PEA and nano titanium dioxide in a mass ratio of 1.85:1.

[0042] A glass fiber cloth preparation method, comprising the following steps: S1 substrate melting: mixing silica, alumina, niobium pentoxide, gallium oxide, cerium oxide, lithium oxide, and zirconium oxide in proportion, and putting them into a melting furnace, the heating rate of the melting furnace is 6.5℃ / min, melting at 1500℃, and keeping the temperature for 3h to obtain a uniform glass melt; S2 wire drawing forming: introducing the glass melt obtained in S1 step into a wire drawing machine die plate, and drawing at 1300℃, the drawing speed of the wire drawing machine is 900m / min, to obtain a glass fiber monofilament with a diameter of 10μm; S3 surface modification: dissolving the composite modifier in a mixed solvent of ethanol and water, the volume ratio of ethanol to water is 8:2; preparing a modifier solution with a mass fraction of 6.5%, and then ultrasonic dispersing, the power of ultrasonic dispersion is 360W, and the time of ultrasonic dispersion is 26min; immersing the glass fiber monofilament prepared in S2 step in the modifier solution, and soaking at 50℃ for 20min; taking out the glass fiber monofilament, and solidifying at 100℃ for 2h to obtain a modified glass fiber monofilament; S4 weaving forming: weaving the modified glass fiber monofilament obtained in S3 step by warp and weft, using a rapier loom, the warp and weft density is 30root / cm, and the weaving speed is 200r / min, to obtain a glass fiber cloth.

[0043] Comparative Example 5: a commercially available conventional glass fiber cloth, SiO2-Al2O3-CaO system Composition: silica 65 parts, alumina 15 parts, calcium oxide 10 parts, magnesium oxide 5 parts, and sodium oxide 5 parts.

[0044] Preparation method: conventional melting (1550℃), wire drawing (1250℃), and weaving.

[0045] The glass fiber cloths prepared in Examples 1~6 and Comparative Examples 1~5 are subjected to performance detection, and the detection results are shown in the following table:

[0046] From the detection data in the above table, it can be seen that: (1) When the proportion of niobium pentoxide increases (such as Example 2: 5 parts of niobium pentoxide and 2 parts of gallium oxide), the glass network density increases, and the tensile strength reaches 850 MPa (the highest in the examples), but the decrease in the proportion of gallium oxide leads to a slight decrease in elasticity, and the elongation at break is 3.8%; when the proportion of gallium oxide increases (such as Example 3: 3 parts of niobium pentoxide and 4 parts of gallium oxide), the network flexibility increases, and the elongation at break reaches 4.0% (the highest in the examples), and the decrease in the proportion of niobium pentoxide leads to a slight decrease in strength, and the tensile strength is 800 MPa; when the proportions of the two are balanced (such as Example 1: 4 parts of niobium pentoxide and 3 parts of gallium oxide), the optimal balance of strength and elasticity is achieved, the tensile strength is 820 MPa, the elongation at break is 3.6%, and the strength retention rate after aging is 92%, which confirms the synergistic effectiveness of the "densification and toughness" of niobium pentoxide and the "flexibility adjustment" of gallium oxide.

[0047] (2) The fluctuation of cerium oxide (1-3 parts) does not significantly affect the oxidation resistance (aging retention rate 90-94%), which indicates that the addition of 1-3 parts can fully play the role of free radical capture and form a stable base material oxidation resistance.

[0048] (3) The change in the amount (1.2-2 parts) and composition (PEA: KH550 = (1.5-2.5):1) of the composite modifier affects the oxidation resistance and water washing stability of the glass fiber cloth: the increase in the proportion of titanium dioxide (such as Example 3) enhances the "double antioxidant center" effect formed by the base material cerium oxide, and the strength retention rate after aging is 94%, although the addition amount of the modifier is only 1.2 parts, but the oxidation resistance is still the best; the increase in the proportion of PEA-KH550 (such as Example 2) enhances the elastic buffer layer effect, and with the addition of 2.0 parts of high addition amount, the tensile strength reaches 850 MPa, but the decrease in the proportion of titanium dioxide reduces the aging retention rate to 90%, but it is still much higher than the prior art; when the composition of the modifier is balanced (such as Example 1), the water washing stability is the best (decay rate 3.2%), which proves that PEA-KH550 "adhesion + elasticity" and titanium dioxide "antioxidation" have a synergistic effect.

[0049] (4) The tensile strength corresponding to the lowest (Example 3) and highest (Example 2) melting temperature is 800 MPa and 850 MPa respectively, with a deviation of only 6.25%, which indicates that 1580-1620℃ can ensure that high-melting-point components form a eutectic phase and avoid unmelted defects; the water washing decay rates corresponding to the lowest (Example 3) and highest (Example 2) curing temperatures are 2.8% and 4.5% respectively, both of which meet the requirement of "decay ≤5%", which proves that 120-140℃ can achieve sufficient crosslinking of the modifier and avoid PEA thermal aging.

[0050] (5) Base material component synergy: Comparative Example 1 vs. Comparative Example 1: After the absence of niobium pentoxide and gallium oxide and the replacement of calcium oxide, the tensile strength decreases from 820 MPa to 650 MPa (a decrease of 20.7%), and the elongation at break decreases from 3.8% to 2.5% (a decrease of 34.2%), proving that the network densification of niobium pentoxide and the flexibility adjustment of gallium oxide are synergistic and are the core of improving the strength and elasticity; Comparative Example 1 vs. Comparative Example 2: Comparative Example 2 has no cerium oxide, and the strength retention rate after aging decreases from 92% to 60% (a decrease of 34.8%), indicating that the redox pair of cerium oxide can effectively capture oxidizing free radicals and is the key to the oxidation resistance at the base material level.

[0051] (6) Surface modification synergy: Comparative Example 1 vs. Comparative Example 3: Comparative Example 3 uses pure KH550 instead of the composite modifier, and the elongation at break decreases from 3.8% to 3.0% (a decrease of 21.1%), the aging retention rate decreases from 92% to 75% (a decrease of 18.5%), and the water washing attenuation rate increases from 3.2% to 8.0% (an increase of 150%), proving that the elasticity contribution of PEA, the oxidation resistance enhancement of nano-titanium oxide, and the adhesion improvement of KH550 are synergistic, optimizing the elasticity, and strengthening the oxidation resistance and stability.

[0052] (7) Preparation parameter synergy: Comparative Example 1 vs. Comparative Example 4: Comparative Example 4 has a too low melting temperature (1500°C), resulting in incomplete melting of niobium pentoxide, and the tensile strength decreases to 720 MPa (a decrease of 12.2%); a too low curing temperature (100°C) results in insufficient cross-linking of the modifier, and the aging retention rate decreases to 78% (a decrease of 15.2%), and the water washing attenuation rate increases to 6.2% (an increase of 93.8%), indicating that the melting temperature needs to match the melting requirements of the components, and the curing temperature needs to ensure the cross-linking of the modifier, and the parameter synergy is the guarantee of performance realization.

[0053] (8) Comprehensive performance advantage: The tensile strength (800-850 MPa), elongation at break (3.6-4.0%), and aging retention rate (90-94%) of Examples 1-6 are significantly better than those of Comparative Example 5 (a commercially available glass fabric), and the water washing stability is also better, proving that the present application realizes the integrated performance of "high strength-high elasticity-superior oxidation resistance" through the multi-dimensional synergy of "base material-modifier-parameters", which cannot be achieved by the prior art.

[0054] In summary, the experimental data of embodiments 1-6 show that the "base material raw material ratio, composite modifier composition, preparation parameter range" defined in the application is scientific and reasonable: the ratio of 3-5 parts of niobium pentoxide and 2-4 parts of gallium oxide in the base material can achieve the synergistic balance of "strength-elasticity"; the addition amount of 1.2-2.0 parts of the composite modifier and the ratio of 1.5-2.5 of PEA-KH550 can take into account the oxidation resistance and stability; and the parameters such as the melting temperature of 1580-1620 DEG C can ensure that the components are fully reacted and the modifier is effectively attached. Through the multi-angle technical improvement of "base material component innovation-composite modifier design-preparation parameter synergy", the glass fiber cloth with high strength, high elasticity and strong oxidation resistance is prepared, which can meet the needs of the fields such as aerospace and high-end electronics which have strict requirements on material performance, and has significant technical value and market potential.

[0055] Obviously, the above embodiments are only examples for the sake of clarity, and are not a limitation on the embodiments. For those skilled in the art, other different forms of changes or variations can be made on the basis of the above description. All embodiments do not need to be exhausted here. The obvious changes or variations derived therefrom are still within the protection scope of the present application.

Claims

1. A fiberglass cloth, characterized in that, It consists of the following components in parts by weight: 60-65 parts silicon dioxide, 15-18 parts aluminum oxide, 3-5 parts niobium pentoxide, 2-4 parts gallium oxide, 1-3 parts cerium oxide, 0.5-1.5 parts lithium oxide, 1-2 parts zirconium oxide, and 1.2-2 parts composite modifier.

2. The fiberglass cloth according to claim 1, characterized in that, The composite modifier is composed of modified PEA and nano-titanium dioxide.

3. The fiberglass cloth according to claim 2, characterized in that, The mass ratio of the modified PEA to nano-titanium dioxide is (1.5~2.5):

1.

4. The fiberglass cloth according to claim 2, characterized in that, The modified PEA is formed by grafting KH550 silane onto PEA to form an amino-terminated polyetheramine grafted with γ-aminopropyltriethoxysilane.

5. A method for preparing fiberglass cloth, characterized in that, Includes the following steps: S1 Substrate Melting: Silica, aluminum oxide, niobium pentoxide, gallium oxide, cerium oxide, lithium oxide, and zirconium oxide are mixed in proportion, added to a melting furnace, melted at 1580~1620℃, and held at that temperature for 2.5~3.5h to obtain a uniform glass melt. S2 Fiber Drawing: The molten glass obtained in step S1 is introduced into the die plate of the fiber drawing machine and drawn at 1280~1320℃ to obtain glass fiber monofilaments with a diameter of 8~12μm; S3 Surface Modification: The composite modifier is dissolved in a mixed solvent of ethanol and water to prepare a modifier solution, and then ultrasonically dispersed; the glass fiber monofilaments obtained in step S2 are immersed in the modifier solution and soaked at 45~55℃ for 15~25min; the glass fiber monofilaments are taken out and cured at 120~140℃ for 1.5~2.5h to obtain modified glass fiber monofilaments; S4 Weaving and Forming: The modified glass fiber monofilaments obtained in step S3 are woven using a rapier loom with a warp and weft density of 28~32 threads / cm and a weaving speed of 180~220r / min to obtain glass fiber cloth.

6. The method for preparing fiberglass cloth according to claim 5, characterized in that, In the S1 substrate melting step, the heating rate of the melting furnace is 5~8℃ / min.

7. The method for preparing fiberglass cloth according to claim 5, characterized in that, In the S2 wire drawing step, the traction speed of the wire drawing machine is 850~950m / min.

8. The method for preparing fiberglass cloth according to claim 5, characterized in that, In the S3 surface modification step, the volume ratio of ethanol to water is 8:2; the mass fraction of the modifier solution is 5-8%.

9. The method for preparing fiberglass cloth according to claim 5, characterized in that, In the S3 surface modification step, the ultrasonic dispersion power is 300~400W.

10. The method for preparing fiberglass cloth according to claim 5, characterized in that, In the S3 surface modification step, the ultrasonic dispersion time is 20~30 min.

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