High performance glass wire drawing process

Abstract

The application discloses a high-performance glass wire drawing process method, relates to the technical field of glass wire drawing, and realizes the whole-process stable control from melt clarification, fiber directional stretching to precise diameter control CV<=8% through the addition of the same component optimization network structure, the combination of the three-section reinforced wire drawing process and online laser diameter measurement closed-loop control, and fundamentally guarantees the structural consistency and high-strength characteristics of the fiber as a reinforcing phase; on the basis, the strategy of combining plasma activation and three-stage aluminum-doped zinc oxide AZO sol gradient spraying-four-temperature-zone step heat treatment is adopted, the fiber surface is activated through an argon-oxygen mixed atmosphere, the uniformity of a multilayer thin coating is improved, and the transformation from precursor decomposition, lattice doping to aluminum-doped zinc oxide AZO nanocrystal dense growth is completed in the programmed temperature rise and controllable atmosphere, and finally, a continuous conductive layer with strong adhesion, stable resistance and perfect crystallization is formed, so that the fiber is endowed with efficient surface conductive function.

Description

Technical Field

[0001] This invention relates to the field of glass drawing technology, and more specifically to a high-performance glass drawing process. Background Technology

[0002] Traditional glass fiber, with its high tensile strength, excellent heat resistance, and chemical stability, has long been widely used as a key reinforcing material in the field of composite materials. Its mainstream preparation process usually uses calcium aluminosilicate or alkali-free glass (E-Glass) as the base formula, with the main components being silicon dioxide (SiO2), Al2O3, CaO, MgO, and B2O3, etc., which are formed by high-temperature melting and platinum spindle drawing.

[0003] However, this traditional system and process exhibit significant limitations when facing modern structure-function integrated applications. Firstly, in terms of the material system, traditional formulations focus on meeting basic mechanical properties and process feasibility. Their glass network structure is relatively simple, making it difficult to simultaneously address the interface requirements of high strength, high modulus, and subsequent functional modifications. The fiber surface is chemically inert, resulting in poor adhesion to functional coatings (such as conductive layers), severely restricting its evolution into functional materials. Secondly, regarding the control of the fiber drawing process, traditional methods have limited precision in controlling melt homogeneity, temperature fluctuations, and drawing tension, leading to large fluctuations in fiber diameter (CV value typically >10%). This diameter inhomogeneity not only directly affects the mechanical property stability of the composite but also poses a fundamental challenge to subsequent uniform functional surface treatment. A more prominent problem is its limited functionality. Traditional glass fibers are strictly defined as "structural reinforcements," lacking inherent electrical, sensing, or other additional functions. To achieve conductivity, the industry typically employs two approaches: one is to coat the fiber surface with an antimony (Sb)-containing ATO coating, which introduces potential heavy metal environmental risks, and the difference in thermal expansion coefficients between the ATO coating and the glass substrate can easily lead to interface stress concentration, making it prone to microcracks and delamination during use; the other is to simply integrate the fiber with external circuits or metal wires, which fails to achieve the functionalization of the material itself, increases the complexity and weight of the system, and makes the interface a weak link in reliability.

[0004] This leads to difficulties in achieving a balance between structural strength, electrical conductivity, and interfacial stability in traditional materials. To address these technical shortcomings, a solution is proposed. Summary of the Invention

[0005] The purpose of this invention is to provide a solution to the aforementioned technical deficiencies.

[0006] The objective of this invention can be achieved through the following technical solution: a high-performance glass drawing process, comprising the following steps: Step S1, glass fiber precursor fabrication: The glass batch containing silicon dioxide (SiO2), aluminum oxide (Al2O3), magnesium carbonate (MgCO3), calcium carbonate (CaCO3), lanthanum oxide (La2O3), and titanium oxide (TiO2) is mixed, melted, and clarified. Then, it is drawn into fibers in three stages through a platinum spindle. The entire drawing process is controlled in a closed loop by an online laser diameter measuring instrument to ensure that the single fiber diameter fluctuation CV value is ≤8%. Step S2, Preparation of aluminum-doped zinc oxide AZO conductive sol: A mixture containing zinc acetate dihydrate Zn(CH3COO)2·2H2O, aluminum nitrate nonahydrate Al(NO3)3·9H2O, glacial acetic acid CH3COOH, acetylacetone C5H8O2, anhydrous ethanol C2H5OH and deionized water H2O is dissolved, ultrasonically aged and filtered to obtain aluminum-doped zinc oxide AZO conductive sol; Step S3, Aluminum-doped zinc oxide (AZO) coated conductive glass fiber composite: The glass fiber filaments obtained in step S1 are subjected to plasma surface activation, and then guided to undergo multi-layer aluminum-doped zinc oxide (AZO) conductive sol gradient spraying through multiple atomizing spraying stations. Subsequently, they are subjected to step heat treatment in a four-temperature zone tunnel furnace, and finally wound up under constant tension. Step S4, preparing the composite coating slurry: preparing a conductive mother liquor containing epoxy resin E51, conductive carbon black, multi-walled carbon nanotubes (MWCNTs) and polyvinylpyrrolidone (PVP); preparing conductive microcapsules with gelatin as the shell material, genipin as the crosslinking agent, and aqueous conductive carbon black slurry as the core; then mixing epoxy resin E51, the conductive mother liquor, γ-aminopropyltriethoxysilane, and the conductive microcapsules and vacuum degassing to obtain the composite coating slurry; Step S5, finished product manufacturing and winding: The aluminum-doped zinc oxide (AZO) coated conductive glass fiber obtained in step S3 is guided through the composite coating slurry obtained in step S4 for dip coating and die shaping. Then, it undergoes a three-stage curing process of UV pre-curing, hot air main curing, and infrared stress relaxation. After passing the inspection, it is wound up under constant tension to obtain the composite filament finished product.

[0007] Furthermore, in step S1, the glass batch consists of 540.0g silicon dioxide (SiO2), 185.0g aluminum oxide (Al2O3), 145.7g magnesium carbonate (MgCO3), 89.3g calcium carbonate (CaCO3), 10.0g lanthanum oxide (La2O3), and 5.0g titanium oxide (TiO2). Its melting and clarifying process is as follows: the temperature is increased to 800°C at 5°C / min, then increased to 1500°C at 8°C / min, and finally increased to 1720°C at 3°C / min and held for 120 minutes. At the same time, vacuum degassing at -0.05MPa is turned on and micro-rotation stirring is performed at a speed of 10 rpm.

[0008] Furthermore, in step S1, the specific process of the three-stage drawing is as follows: the initial drawing stage draws the wire at a traction speed of 0.1 m / min, assisted by cooling air at 40℃, and shapes it to 30-50 μm; the middle stage fine drawing increases the linear speed to 0.8 m / min, cools at 30℃, and draws it to 15-25 μm; the final stage sizing increases the linear speed to 1.5 m / min, forces cooling at 25℃, and finally controls the single filament diameter to 10±1 μm.

[0009] Further, in step S2, the preparation of the aluminum-doped zinc oxide (AZO) conductive sol is as follows: 10.0 g of zinc acetate dihydrate (Zn(CH3COO)2·2H2O) and 180.0 mL of anhydrous ethanol (C2H5OH) are weighed and dissolved by stirring; then 0.38 g of aluminum nitrate nonahydrate (Al(NO3)3·9H2O) is weighed and dissolved in 20 mL of anhydrous ethanol (C2H5OH), followed by the addition of 1.2 mL of glacial acetic acid (CH3COOH) and 0.2 g of acetylacetone (C5H8O2), and stirred for 10 minutes; 6.0 mL of deionized water (H2O) is measured and added in three portions, with each addition followed by ultrasonic treatment at 400 watts for 5 minutes, followed by standing and aging for 60 minutes, and finally filtered through a 0.45 μm filter membrane to obtain the final product.

[0010] Furthermore, in step S3, the process parameters for plasma surface activation are: power 28 watts, processing time 8 seconds, argon (Ar) and oxygen (O2) mixed atmosphere, and pressure 80 Pa; the multi-layer gradient spraying is a three-coat spraying, with the following process parameters in sequence: primer spraying pressure 0.20 MPa, aluminum-doped zinc oxide (AZO) conductive sol flow rate 1.0 ml / min; intermediate coat is applied after pre-drying at 80°C for 2 minutes, with a spraying pressure of 0.22 MPa and a flow rate of 1.5 ml / min; top coat is applied after pre-drying again, with a spraying pressure of 0.18 MPa and a flow rate of 1.0 ml / min.

[0011] Furthermore, in step S3, the conditions for the four-temperature zone stepped heat treatment are as follows: the first temperature zone is 120°C for 10 minutes; the second temperature zone is 300°C for 15 minutes; the third temperature zone is 420°C for 25 minutes, and the treatment atmosphere is a mixed gas of nitrogen (N2) and oxygen (O2) in a volume ratio of 9:1; the fourth temperature zone is gradually cooled from 250°C to 100°C for 30 minutes.

[0012] Further, in step S4, the preparation method of the conductive microcapsules is as follows: 0.40g of gelatin is dissolved in 19.6g of deionized water (H2O) to obtain a shell material solution with a mass fraction of 2%; 1.5g of the shell material solution is mixed with 1.5g of aqueous conductive carbon black slurry as the inner phase, and added dropwise to 150ml of preheated liquid paraffin at 40-45℃. After mechanical stirring at 500 rpm, the mixture is dispersed at a high speed of 4000 rpm for 3 minutes to form a primary emulsion; while maintaining low-speed stirring at 150 rpm, 0.04g of genipin is added, and crosslinking is performed at 37℃ for 12 hours; after crosslinking, the upper oil phase is discarded, and the mixture is treated with n-hexane (C6H2O). 14 The microcapsules were washed three times each with deionized water (H2O) and then centrifuged to obtain wet conductive microcapsules.

[0013] Furthermore, in step S5, the specific process parameters for the three-stage curing are as follows: UV pre-curing uses a UV-LED light source with a wavelength of 365 nm and an intensity of 80 mW / cm², exposed for 5 seconds; hot air main curing is performed in an 80℃ hot air circulating oven for 5 minutes; infrared stress relaxation is performed under 90℃ short-wave infrared light for 30 seconds; the passing standard is: composite filament outer diameter 150±5 μm, resistance value 10³-10 5 Ohms / cm.

[0014] The present invention has the following beneficial effects: This invention optimizes the network structure by adding components such as La2O3 and TiO2, and combines a three-stage enhanced fiber drawing process with online laser diameter measurement closed-loop control to achieve stable control of the entire process from melt clarification and fiber directional stretching to precise diameter control (CV≤8%), fundamentally ensuring the structural consistency and high strength characteristics of the fiber as the reinforcing phase. Based on this, a strategy combining plasma activation and a three-stage aluminum-doped zinc oxide (AZO) sol gradient spraying followed by four-temperature-zone stepped heat treatment is employed. The fiber surface is activated by an argon-oxygen mixed atmosphere, and multi-layer thin coating improves film uniformity. The transformation from precursor decomposition and Al³⁺ lattice doping to dense growth of aluminum-doped zinc oxide (AZO) nanocrystals is completed in a programmed temperature rise and N2 / O2 controlled atmosphere, ultimately forming a continuous conductive layer with strong adhesion, stable resistance, and perfect crystallization, endowing the fiber with highly efficient surface conductivity.

[0015] Furthermore, in the construction of the composite system, a highly conductive mother liquor was prepared by synergistic dispersion of conductive carbon black, multi-walled carbon nanotubes (MWCNTs), and polyvinylpyrrolidone (PVP). This mother liquor was then compounded with gelatin-genipin crosslinked microcapsules, simultaneously achieving the construction of a three-dimensional conductive network and the integration of damage self-diagnosis functions within an epoxy resin matrix. The microcapsules, acting as stress-response units, can actively release their conductive cores when the fibers are damaged, inducing a sudden change in resistance and thus enabling early detection of internal material damage. Finally, a three-stage composite filament forming process—UV pre-curing, hot air curing, and infrared stress relaxation—effectively regulates the interfacial stress state while efficiently forming a film, ensuring the structural integrity between functional layers. This results in a composite filament with excellent tensile strength, stable high conductivity, sensitive self-diagnosis capabilities, and good environmental durability, successfully achieving sensing, conductivity, and high strength to meet the application requirements of high-end integrated electronic structures. This solves the systemic technical problem of the difficulty in synergizing structural strength, conductivity, and interfacial stability in traditional materials. Detailed Implementation

[0016] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0017] The following are some of the core materials used in this application: In this application, the following materials were purchased: silicon dioxide (from Hebei Jizhong New Materials Co., Ltd.); alumina (from Hebei Jizhong New Materials Co., Ltd.); magnesium carbonate (from Hebei Jizhong New Materials Co., Ltd.); calcium carbonate (from Hebei Jizhong New Materials Co., Ltd.); lanthanum oxide (from Hebei Jizhong New Materials Co., Ltd.); titanium oxide (from Hebei Jizhong New Materials Co., Ltd.); zinc acetate dihydrate (from Shanghai Aladdin Biochemical Technology Co., Ltd.); aluminum nitrate nonahydrate (from Shanghai Aladdin Biochemical Technology Co., Ltd.); glacial acetic acid (from Shanghai Aladdin Biochemical Technology Co., Ltd.); and acetylene (from Hebei Jizhong New Materials Co., Ltd.). Acetone was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.; E51 epoxy resin was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.; conductive carbon black was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.; multi-walled carbon nanotubes (MWCNTs) were purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.; polyvinylpyrrolidone was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.; gelatin was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.; genipin was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.; and γ-aminopropyltriethoxysilane was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd. Example

[0018] This embodiment provides a high-performance glass drawing process, including the following steps: Step S1, Fabrication of glass fiber precursor: First, weigh out 540.0g SiO2, 185.0g Al2O3, 145.7g MgCO3, and 89.3g CaCO3, which are converted to 50.0g CaO, 10.0g La2O3, and 5.0g TiO2. Place them in a high-speed mixer and dry mix at 300rpm for 30 minutes to obtain a uniform glass preform. Weigh out 1000.0g of the above glass preform, place it in a platinum crucible, and transfer it to a high-temperature furnace. Increase the temperature to 800℃ at 5℃ / min, then to 1500℃ at 8℃ / min, and finally to 1720℃ at 3℃ / min, holding for 120 minutes. Simultaneously, activate the vacuum degassing setting at -0.05MPa and perform micro-stirring at 10rpm. After clarification, stabilize the melt temperature at 1700±5℃, preparing for wire drawing.

[0019] The melt is poured into a 200-hole platinum spinneret preheated to 1700°C and subjected to a three-stage wire drawing process: Initial drawing: The wire is drawn at a speed of 0.1 m / min, assisted by cooling air at 40℃, and shaped to 30-50 μm.

[0020] Mid-stage fine drawing: Increase the linear speed to 0.8 m / min, cool at 30℃, and draw to a thickness of 15-25 μm.

[0021] Final sizing: The linear velocity is increased to 1.5 m / min, and forced cooling is performed at 25℃ to precisely control the single filament diameter to 10 ± 1 μm. The entire glass fiber drawing process is controlled in a closed loop by an online laser diameter gauge to ensure that the diameter fluctuation CV value is ≤8%, thus guaranteeing the uniformity and consistency of the glass fiber diameter.

[0022] Step S2, Preparation of aluminum-doped zinc oxide (AZO) conductive sol First, weigh out 10.0 g of Zn(CH3COO)2·2H2O and 180.0 mL of anhydrous ethanol, and stir to dissolve. Then, weigh out 0.38 g of Al(NO3)3·9H2O and dissolve it in 20 mL of anhydrous ethanol. Next, add 1.2 mL of glacial acetic acid and 0.2 g of acetylacetone sequentially, and stir for 10 minutes. Then, add 6.0 mL of deionized water in three portions, sonicating for 5 minutes after each addition using a 400W ultrasonic machine. Allow to stand for 60 minutes, then filter through a 0.45 μm filter membrane to obtain aluminum-doped zinc oxide (AZO) conductive sol.

[0023] Step S3, Aluminum-doped zinc oxide (AZO) coated conductive glass fiber composite: Glass fiber filaments were continuously passed through a 28W plasma chamber at a linear velocity of 1.2 m / min for 8 seconds. An argon and oxygen mixed atmosphere was first established within the plasma chamber, with a pressure set at 80 Pa. The fibers were then guided sequentially through three atomizing spray stations. Primer application: Spraying pressure 0.20MPa, solvent flow rate 1.0mL / min.

[0024] Secondary coat: After pre-drying at 80℃ for 2 minutes, spray at a pressure of 0.22MPa and a flow rate of 1.5mL / min.

[0025] Final coat: After pre-drying again, spray at a pressure of 0.18 MPa and a flow rate of 1.0 mL / min.

[0026] After the glass fibers undergoing the three coating processes described above are placed in a four-zone tunnel furnace, the temperatures and times of the four zones are set sequentially for a heating-cooling process: 120℃ / 10min → 300℃ / 15min → 420℃ / 25min (N2 / O2=9:1) → 250℃ to 100℃ gradient cooling / 30min. This process yields aluminum-doped zinc oxide (AZO) coated conductive glass fibers, which are wound onto a spool at a constant tension of 2.0 cN / tex and temporarily stored for later use. Aluminum-doped zinc oxide (AZO) is zinc oxide doped with aluminum.

[0027] In the first temperature zone, the wet film dries slowly at a lower temperature to prevent solvent boiling, which could cause bubbles or cracks in the coating. Simultaneously, the sol begins a preliminary condensation reaction, forming a solid gel network, which initially "sets" the coating, thereby removing volatile solvents such as ethanol and water from the sol. The second temperature zone treatment thoroughly decomposes and burns away organic groups such as acetate and nitrate ions, as well as residual dispersants in the precursor. If these organic compounds are not completely removed, they will carbonize and form black impurities, severely affecting the conductivity and transparency of the coating. At this temperature, residual water of crystallization is also completely removed. In the third temperature zone, at sufficiently high energies, zinc oxide (ZnO) atoms acquire migration capabilities and arrange themselves into a regular crystal structure, thus achieving excellent semiconductor properties. Simultaneously, the particles fuse together, reducing porosity and forming a continuous, dense, and robust thin film. Aluminum atoms (Al³⁺) successfully enter the zinc oxide lattice at high temperatures, replacing zinc ions (Zn²⁺) and providing free conductive electrons. N₂ serves as the primary protective gas to prevent excessive oxidation; a small amount of O₂ is used to precisely control the oxygen vacancy concentration in the lattice, avoiding a decrease in conductivity due to too many or too few oxygen vacancies.

[0028] In the fourth temperature zone treatment, the aluminum-doped zinc oxide (AZO) conductive sol and the glass fiber substrate have different coefficients of thermal expansion. Rapidly cooling directly from 420℃ to room temperature would generate significant internal stress due to uneven shrinkage. A preset gradient cooling process, slowly decreasing from 250℃ to 100℃, allows the coating and substrate to shrink at a near-synchronous rate, maximizing the release of internal stress and preventing the coating from cracking, wrinkling, or peeling off the fiber due to stress. During slow cooling, the crystal lattice has the opportunity to fine-tune, arranging atoms to more stable positions. Some unstable defects formed at high temperatures are eliminated. If rapidly cooled, these defects would be "frozen" inside the material, leading to unstable performance, high resistivity, and easy drift. This results in a more perfect crystal structure and more stable conductivity in the coating. The slow cooling also creates a low-stress state, ensuring a good interface between the coating and the fiber substrate, thus achieving stronger adhesion. In this way, by first heating in four temperature zones and then gradually cooling down, the loose, amorphous aluminum-doped zinc oxide (AZO) sol wet film coated on the fiber surface is transformed into a dense, crystalline aluminum-doped zinc oxide (AZO) nanocrystalline coating with conductive function. Step S4: Prepare composite coating slurry Weigh out 75.0g of epoxy resin E51 and preheat it to 45℃. Add 15.0g of conductive carbon black, 5.0g of multi-walled carbon nanotubes (MWCNTs), and 5.0g of dispersant polyvinylpyrrolidone (PVP). Place the mixture in a stirred tank and mix at 100 rpm for 10 minutes. Transfer the mixture to a three-roll mill and circulate it through the mill three times, passing it through rollers with gaps of 50μm, 20μm, and 10μm. Finally, disperse the mixture in a high-shear emulsifier at 5000 rpm for 15 minutes, keeping the temperature below 40℃, to obtain a conductive mother liquor.

[0029] First, 0.40 g of gelatin was dissolved in 19.6 g of deionized water preheated to 55°C to obtain a 2 wt% shell material solution. Then, 1.5 g of the shell material solution was mixed with 1.5 g of aqueous conductive carbon black slurry to form the internal phase mixture. This mixture was then slowly added dropwise to 150 mL of liquid paraffin preheated to 40-45°C while simultaneously stirring at 500 rpm. After complete addition, the mixture was sheared at 4000 rpm for 3 minutes to form a primary emulsion. The emulsion system was then stirred at a low speed of 150 rpm. Next, 0.04 g of the crosslinking agent Genipin was added to the primary emulsion, and crosslinking was performed at 37°C for 12 hours. After crosslinking, the upper oil phase was discarded, and the mixture was washed three times each with hexane and deionized water, then centrifuged to obtain wet conductive microcapsules.

[0030] Finally, weigh out 100.0g of epoxy resin E51, 20.0g of conductive mother liquor, and 1.5g of coupling agent γ-aminopropyltriethoxysilane. Stir at 300rpm for 15 minutes, then weigh out 15.0g of wet conductive microcapsules and slowly add them at a rate of 1.0g / min. Reduce the stirring speed to 150rpm and continue stirring for 20 minutes. Subsequently, degas under vacuum at -0.095MPa for 20 minutes to obtain the composite coating slurry.

[0031] Step S5: Finished Product Production and Rolling Aluminum-doped zinc oxide (AZO) coated conductive glass fibers are guided through a composite coating slurry impregnation tank at a linear velocity of 1.0 m / min, and then shaped using a sapphire die with an inner diameter of 150 μm, controlling the wet film thickness to be 30-50 μm. Next, they enter a three-stage curing channel: Step 1 UV pre-curing: 365nm UV-LED, intensity 80mW / cm², exposure for 5 seconds.

[0032] The second step is hot air curing: 80℃ hot air circulating oven, for 5 minutes.

[0033] The third step is infrared stress relaxation: 90℃ short-wave infrared treatment for 30 seconds.

[0034] The cured composite filament is sequentially passed through a laser diameter gauge (preset target outer diameter μm) and an eddy current resistivity meter (preset target resistance Ω / cm). After passing the tests, it is wound onto a spool by a high-precision constant tension winding machine with a tension of 2.0 cN / tex. The machine automatically prompts for sampling every 500 meters of winding, ultimately yielding a high-strength, highly conductive, and environmentally friendly composite filament product.

[0035] The cured composite filaments were then passed sequentially through a laser diameter gauge and an eddy current resistivity meter, with the target outer diameter preset to 150±5μm and the target resistance to be 10³-10 μm, respectively. 5 Ω / cm. After passing the inspection, the wire is wound onto a spool by a high-precision constant tension winding machine at a tension of 2.0 cN / tex. The machine automatically prompts for sampling every 500 meters of winding, ultimately yielding a high-strength, high-conductivity, environmentally friendly composite filament product. Example

[0036] A high-performance glass drawing process, Adjust step S1 of Example 1 to control the monofilament diameter to 12±1μm; The S2 process of Example 1 was adjusted by reducing the amount of Zn(CH3COO)2·2H2O to 8.0g and the amount of Al(NO3)3·9H2O to 0.25g to ensure 2at% Al doping; The temperature and time of the four temperature zones in step S3 of Example 1 are adjusted sequentially as follows: 120℃ / 10min → 280℃ / 15min → 400℃ / 20min → gradient cooling from 250℃ to 100℃ / 30min. The other steps are the same as in Example 1. Example

[0037] Step S1, Fabrication of glass fiber precursor: First, weigh out 580.0g SiO2, 150.0g Al2O3, 125.2g MgCO3 (converted to 60.0g MgO), 71.4g CaCO3 (converted to 40.0g CaO), 5.0g La2O3, and 5.0g TiO2. Place them in a high-speed mixer and dry mix at 300rpm for 30 minutes to obtain a uniform glass preform. Subsequent melting, clarification, and wire drawing processes are the same as in Example 1. Wire drawing is performed in three stages: Initial stage: wire is drawn at a traction speed of 0.15m / min, assisted by cooling air at 40℃, and shaped to 30-50μm; Middle stage: fine drawing: the linear speed is increased to 1.0m / min, cooled at 30℃, and drawn thinner to 15-25μm; Final stage: the linear speed is increased to 2.0m / min, forced cooling at 25℃, and the final precise control of the single wire diameter to 15±2μm. The entire process is controlled by an online laser diameter gauge in a closed loop, ensuring that the diameter fluctuation CV value is ≤10%.

[0038] Step S2, Preparation of aluminum-doped zinc oxide (AZO) conductive sol: First, weigh out 12.0 g of Zn(CH3COO)2·2H2O and 180.0 mL of anhydrous ethanol, and stir to dissolve. Then, weigh out 0.45 g of Al(NO3)3·9H2O and dissolve it in 20 mL of ethanol. Next, add 1.2 mL of glacial acetic acid and 0.2 g of acetylacetone sequentially, and stir for 10 minutes. Then, add 6.0 mL of deionized water in three portions, sonicating for 5 minutes after each addition using a 400W ultrasonic machine. Allow to stand for 60 minutes, then filter through a 0.45 μm filter membrane to obtain aluminum-doped zinc oxide (AZO) conductive sol.

[0039] Step S3, Aluminum-doped zinc oxide (AZO) coated conductive glass fiber composite: The coating process consists of four coats: first, a primer coat, sprayed at a pressure of 0.20 MPa and a solvent flow rate of 1.0 mL / min; second, an intermediate coat, pre-dried at 80°C for 2 minutes, sprayed at a pressure of 0.22 MPa and a flow rate of 1.5 mL / min; third, an intermediate coat, pre-dried again, sprayed at a pressure of 0.22 MPa and a flow rate of 1.5 mL / min; and finally, a top coat, pre-dried, sprayed at a pressure of 0.18 MPa and a flow rate of 1.0 mL / min.

[0040] The heat treatment regime was the same as in Example 1: 120℃ / 10min → 300℃ / 15min → 420℃ / 25min (N2 / O2=9:1) → gradient cooling from 250℃ to 100℃ / 30min. After treatment, aluminum-doped zinc oxide (AZO) coated conductive glass fibers were obtained, which were wound onto a spool at a constant tension of 2.0 cN / tex and temporarily stored for later use.

[0041] Step S4, prepare the composite coating slurry: Weigh out 70.0g of epoxy resin E51 and preheat it to 45℃. Add 18.0g of conductive carbon black, 7.0g of multi-walled carbon nanotubes (MWCNTs), and 5.0g of dispersant polyvinylpyrrolidone (PVP). Place the mixture in a stirred tank and mix at 100 rpm for 10 minutes. Transfer the mixture to a three-roll mill and circulate it through the mill three times, passing it through rollers with gaps of 50μm, 20μm, and 10μm. Finally, disperse the mixture in a high-shear emulsifier at 5000 rpm for 15 minutes, keeping the temperature below 40℃, to obtain a conductive mother liquor.

[0042] The microcapsules were prepared using the gelatin-genipin system of Example 1. By controlling the microfluidic parameters, the microcapsule particle size was controlled to be 10-30 μm.

[0043] Finally, weigh out 100.0g of epoxy resin E51, 20.0g of conductive mother liquor, and 1.5g of coupling agent γ-aminopropyltriethoxysilane. Stir at 300rpm for 15 minutes, then weigh out 15.0g of wet conductive microcapsules and slowly add them at a rate of 1.0g / min. Reduce the stirring speed to 150rpm and continue stirring for 20 minutes. Subsequently, degas under vacuum at -0.095MPa for 20 minutes to obtain the composite coating slurry.

[0044] Step S5, Finished Product Production and Rewinding: The process is the same as in Example 1, controlling the wet film thickness of the composite slurry to be 40-60 μm. Target surface resistivity: 1 × 10⁻⁶ 4 -5×10 5 Ω / □. The other steps are the same as in Example 1, ultimately yielding a high-conductivity, medium-strength composite filament. Ω / □ It should be noted that the unit is ohms per square meter (Ω / □), which measures the conductivity of two-dimensional thin-film materials. The purpose here is to focus only on thickness and the conductivity properties of the material itself, thus allowing for a fair comparison of the conductivity of different films. Comparative Example 1: Uncoated glass fiber composite filament The preparation and coating process of aluminum-doped zinc oxide (AZO) coating in step S2 and the heat treatment process of aluminum-doped zinc oxide (AZO) coating in step S3 are omitted.

[0045] In step S4, 100.0 g of epoxy resin E51 and 1.5 g of coupling agent γ-aminopropyltriethoxysilane were weighed and stirred at 300 rpm for 15 minutes. Subsequently, the mixture was degassed under vacuum at -0.095 MPa for 20 minutes to obtain the basic composite slurry. It should be noted that conductive mother liquor and microcapsules are not added here. In step S5, uncoated glass fiber filaments are guided through a basic composite slurry impregnation tank at a linear speed of 1.0 m / min, and then shaped using a sapphire die with an inner diameter of 150 μm, controlling the wet film thickness to be 30-50 μm. This ultimately yields uncoated glass fiber composite filaments.

[0046] The other steps are the same as in Example 1. This comparative example directly uses uncoated glass fiber and base resin to compare and verify the aluminum-doped zinc oxide (AZO) coating and conductive network.

[0047] Comparative Example 2: Carbon black conductive composite filament only

[0048] Specific implementation steps

[0049] Step S4: Prepare conductive carbon black conductive paste and composite coating paste: Weigh 80.0g of epoxy resin E51 and preheat to 45℃, then add 20.0g of conductive carbon black and 5.0g of dispersant polyvinylpyrrolidone (PVP). Mix in a stirred tank at 100 rpm for 10 minutes. Transfer to a three-roll mill and circulate through 50μm, 20μm, and 10μm rollers three times. Finally, disperse using a high-shear emulsifier at 5000 rpm for 15 minutes, with the temperature controlled below 40℃, to obtain conductive carbon black conductive mother liquor. Multi-walled carbon nanotubes (MWCNTs) are not added and microcapsules are not prepared during this process. Directly weigh 100.0g of epoxy resin E51, 20.0g of conductive carbon black conductive mother liquor, and 1.5g of coupling agent γ-aminopropyltriethoxysilane, and stir at 300 rpm for 15 minutes. Then degas under vacuum at -0.095 MPa for 20 minutes, and follow the same steps as in Example 1 to obtain a composite coating slurry. This comparative example uses only conductive carbon black as a conductive filler, without adding multi-walled carbon nanotubes (MWCNTs) or microcapsules, to compare and verify the synergistic effect between MWCNTs and microcapsules.

[0050] Comparative Example 3: Specific Implementation Steps for Traditional Antimony-Doped Tin Oxide (ATO) Coated Composite Wire In step S2, first weigh 8.0 g of SnCl4·5H2O and 180.0 mL of anhydrous ethanol, and stir to dissolve. Then weigh 0.32 g of antimony trichloride (SbCl3) and dissolve it in 20 mL of ethanol. Next, add 1.5 mL of hydrochloric acid and 0.2 g of acetylacetone sequentially, and stir for 10 minutes. Measure 5.0 mL of deionized water and add it in three portions, sonicating for 5 minutes after each addition using a 400W ultrasonic machine. Allow to stand for 60 minutes, then filter through a 0.45 μm filter membrane to obtain antimony-doped tin oxide (ATO) conductive sol.

[0051] The four-temperature zone heat treatment regime in step S3 was adjusted to: 120℃ / 10min → 300℃ / 15min → 500℃ / 25min (the N2 / O2 atmosphere was removed here, and it became a normal air atmosphere) → gradient cooling from 250℃ to 100℃ / 30min. After treatment, antimony-doped tin oxide (ATO) coated conductive glass fiber was obtained, which was wound onto a spool at a constant tension of 2.0 cN / tex and temporarily stored for later use.

[0052] The other steps are the same as in Example 1. The final product is a conventional antimony-doped tin oxide (ATO) coated composite wire.

[0053] This comparative example uses traditional antimony-doped tin oxide (ATO) instead of environmentally friendly aluminum-doped zinc oxide (AZO) coating.

[0054] test group Conductivity, tensile properties, and elasticity are tested according to the following standards: GB / T15738-2008 "Test Method for Resistivity of Conductive and Antistatic Fiber Reinforced Plastics", GB / T3362-2005 "Test Method for Tensile Properties of Carbon Fiber Multifilament", and GB / T10700-2006 "Test Method for Elastic Modulus of Fine Ceramics - Bending Method". Higher values ​​indicate better performance for the target product. The specific table is as follows: Example 1 5.0×104–5.0×105 4.5 850 45 100.0 Example 2 5.0×106–1.0×108 6.5 830 44 91.3 Example 3 1.0×104–5.0×105 4.5 780 42 88.8 Comparative Example 1 >1.0×10¹⁰ (insulation) 0.0 820 43 61.3 Comparative Example 2 1.0×106–1.0×107 6.0 800 41 82.5 Comparative Example 3 3.0×104–8.0×105 4.4 840 44 92.1 Data Analysis: Comparative analysis of the performance data revealed that the high-performance composite wire prepared in Example 1 of this invention achieved a tensile strength of 850 MPa and an elastic modulus of 45 GPa, while maintaining a stable surface resistivity of 5.0 × 10⁻⁶. 4 -5.0×10 5 Within the Ω / □ range, and possessing a self-diagnostic sensitivity with a resistance change ≥15 times, all performance indicators are superior to the comparative group. This indicates that: In Comparative Example 1, the construction of the AZO conductive coating and the carbon-based conductive network was cancelled, resulting in the lack of continuous conductive pathways on the surface of the glass fiber. The material completely lost its conductive function. At the same time, due to the lack of toughening effect of microcapsules, the fracture toughness and damage self-diagnosis ability of the composite filament were significantly deteriorated. In Comparative Example 2, only conductive carbon black was used without the synergistic system of multi-walled carbon nanotubes (MWCNTs) and microcapsules. As a result, the conductive network was formed only by point contact, resulting in insufficient electron transport efficiency and poor resistance stability. At the same time, due to the lack of stress buffering and crack induction effect of microcapsules, the material could not achieve damage self-diagnosis when under stress, and its toughness and functional integrity were compromised. In Comparative Example 3, if traditional antimony-containing ATO is used to replace the environmentally friendly AZO coating, a certain level of conductivity can be obtained. However, the presence of the heavy metal antimony in the system leads to poor environmental compatibility of the material, which does not meet the requirements of green environmental protection. Furthermore, the thermal stress matching between the coating and the fiber matrix during high-temperature treatment is poor, which affects the long-term interface stability. In conclusion, this invention demonstrates that the key factors for achieving the integrated strength, conductivity, and self-diagnostic capability of composite filaments are the high-alumina silicate glass formulation design, the controllable construction of AZO nano-coatings, and the multi-level synergy of conductive carbon black-multi-walled carbon nanotube (MWCNT) conductive network and gelatin-genipin microcapsules. Compared with the comparative group, the embodiments show significant advantages in mechanical properties, electrical properties, and functional characteristics, verifying the feasibility, innovation, and application prospects of this technical solution in the field of structure-function integrated composite materials.

[0055] The above description is merely an example and illustration of the structure of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described, or use similar methods to replace them, as long as they do not deviate from the structure of the invention or exceed the scope defined in the claims, all of which should fall within the protection scope of the present invention.

[0056] In the description of this specification, references to terms such as "an embodiment," "example," and "specific example" indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0057] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to specific implementations. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. A high-performance glass drawing process, comprising the following steps: Step S1, glass fiber precursor fabrication: The glass batch containing silicon dioxide (SiO2), aluminum oxide (Al2O3), magnesium carbonate (MgCO3), calcium carbonate (CaCO3), lanthanum oxide (La2O3), and titanium oxide (TiO2) is mixed, melted, and clarified. It is then drawn in three stages using a platinum spinneret. The entire drawing process is controlled in a closed loop by an online laser diameter measuring instrument to ensure that the single filament diameter fluctuation CV value is ≤8%. Its characteristic is that it further includes: Step S2, Preparation of aluminum-doped zinc oxide AZO conductive sol: A mixture containing zinc acetate dihydrate Zn(CH3COO)2·2H2O, aluminum nitrate nonahydrate Al(NO3)3·9H2O, glacial acetic acid CH3COOH, acetylacetone C5H8O2, anhydrous ethanol C2H5OH and deionized water H2O is dissolved, ultrasonically aged and filtered to obtain aluminum-doped zinc oxide AZO conductive sol; Step S3, Aluminum-doped zinc oxide (AZO) coated conductive glass fiber composite: The glass fiber filaments obtained in step S1 are subjected to plasma surface activation, and then guided to undergo multi-layer aluminum-doped zinc oxide (AZO) conductive sol gradient spraying through multiple atomizing spraying stations. Subsequently, they are subjected to step heat treatment in a four-temperature zone tunnel furnace, and finally wound up under constant tension. Step S4, preparing the composite coating slurry: preparing a conductive mother liquor containing epoxy resin E51, conductive carbon black, multi-walled carbon nanotubes (MWCNTs) and polyvinylpyrrolidone (PVP); preparing conductive microcapsules with gelatin as the shell material, genipin as the crosslinking agent, and aqueous conductive carbon black slurry as the core; then mixing epoxy resin E51, the conductive mother liquor, γ-aminopropyltriethoxysilane, and the conductive microcapsules and vacuum degassing to obtain the composite coating slurry; Step S5, finished product manufacturing and winding: The aluminum-doped zinc oxide (AZO) coated conductive glass fiber obtained in step S3 is guided through the composite coating slurry obtained in step S4 for dip coating and die shaping. Then, it undergoes a three-stage curing process of UV pre-curing, hot air main curing, and infrared stress relaxation. After passing the inspection, it is wound up under constant tension to obtain the composite filament finished product.

2. The high-performance glass drawing process according to claim 1, characterized in that, In step S1, the glass batch material is composed of 540.0g silicon dioxide (SiO2), 185.0g aluminum oxide (Al2O3), 145.7g magnesium carbonate (MgCO3), 89.3g calcium carbonate (CaCO3), 10.0g lanthanum oxide (La2O3) and 5.0g titanium oxide (TiO2). Its melting and clarifying process is as follows: the temperature is raised to 800℃ at 5℃ / min, then raised to 1500℃ at 8℃ / min, and finally raised to 1720℃ at 3℃ / min and held for 120 minutes. At the same time, vacuum degassing at -0.05MPa is turned on and micro-rotation stirring is performed at a speed of 10 rpm.

3. The high-performance glass drawing process according to claim 1, characterized in that, In step S1, the specific process of the three-stage drawing is as follows: the initial drawing stage draws the wire at a traction speed of 0.1 m / min, with cooling air assistance at 40℃, and shapes it to 30-50 μm; the middle stage fine drawing increases the linear speed to 0.8 m / min, cools at 30℃, and draws it thinner to 15-25 μm; the final stage sizing increases the linear speed to 1.5 m / min, forces cooling at 25℃, and finally controls the single filament diameter to 10±1 μm.

4. The high-performance glass drawing process according to claim 1, characterized in that, In step S2, the preparation of the aluminum-doped zinc oxide (AZO) conductive sol is as follows: Weigh 10.0 g of zinc acetate dihydrate (Zn(CH3COO)2·2H2O) and 180.0 mL of anhydrous ethanol (C2H5OH), and stir to dissolve; then weigh 0.38 g of aluminum nitrate nonahydrate (Al(NO3)3·9H2O) and dissolve it in 20 mL of anhydrous ethanol (C2H5OH), then add 1.2 mL of glacial acetic acid (CH3COOH) and 0.2 g of acetylacetone (C5H8O2) sequentially, and stir for 10 minutes; measure 6.0 mL of deionized water (H2O) and add it in three portions, sonicating it for 5 minutes after each addition using a 400-watt machine, allowing it to stand and age for 60 minutes, and then filtering it through a 0.45 μm filter membrane to obtain the final product.

5. The high-performance glass drawing process according to claim 1, characterized in that, In step S3, the process parameters for plasma surface activation are: power 28 watts, processing time 8 seconds, argon (Ar) and oxygen (O2) mixed atmosphere, and pressure 80 Pa. The gradient spraying of the multilayer aluminum-doped zinc oxide (AZO) conductive sol consists of three coats, with the following process parameters: primer spraying pressure 0.20 MPa, aluminum-doped zinc oxide (AZO) conductive sol flow rate 1.0 mL / min; intermediate coat spraying after pre-drying at 80°C for 2 minutes, spraying pressure 0.22 MPa, flow rate 1.5 mL / min; and top coat spraying after pre-drying again, spraying pressure 0.18 MPa, flow rate 1.0 mL / min.

6. The high-performance glass drawing process according to claim 1, characterized in that, In step S3, the conditions for the four-zone stepped heat treatment are as follows: first zone 120℃ for 10 minutes; second zone 300℃ for 15 minutes; third zone 420℃ for 25 minutes, with the treatment atmosphere being... A mixture of nitrogen (N2) and oxygen (O2) in a volume ratio of 9:1; the fourth temperature zone is gradually cooled from 250℃ to 100℃ over a period of 30 minutes.

7. The high-performance glass drawing process according to claim 1, characterized in that, In step S4, the preparation method of the conductive microcapsules is as follows: 0.40g of gelatin is dissolved in 19.6g of deionized water (H2O) to obtain a shell material solution with a mass fraction of 2%; 1.5g of the shell material solution is mixed with 1.5g of aqueous conductive carbon black slurry as the inner phase, and added dropwise to 150ml of preheated liquid paraffin at 40-45℃. After mechanical stirring at 500 rpm, the mixture is dispersed at a high speed of 4000 rpm for 3 minutes to form a primary emulsion; while maintaining low stirring at 150 rpm, 0.04g of genipin is added, and crosslinking is performed at 37℃ for 12 hours; after crosslinking, the upper oil phase is discarded, and the mixture is treated with n-hexane (C6H2O). 14 The microcapsules were washed three times each with deionized water (H2O) and then centrifuged to obtain wet conductive microcapsules.

8. The high-performance glass drawing process according to claim 1, characterized in that, In step S5, the specific process parameters for the three-stage curing are as follows: UV pre-curing uses a UV-LED light source with a wavelength of 365 nm and an intensity of 80 mW / cm², exposed for 5 seconds; hot air main curing is performed in an 80℃ hot air circulating oven for 5 minutes; infrared stress relaxation is performed under 90℃ short-wave infrared light for 30 seconds; the passing standard is: composite filament outer diameter 150±5 μm, resistance value 10³-10 5 Ohms per centimeter.

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