High-strength wear-resistant nanocomposite fiber fabric and preparation method thereof

Abstract

The application discloses a kind of high-strength wear-resistant nanometer composite fiber fabric and preparation method thereof, it is related to textile fabric technical field, after pretreatment, polyvinylpyrrolidone is dissolved in the mixed solution of deionized water and dimethylformamide with volume ratio of 7:3, after adding modified silicon dioxide and modified titanium dioxide, polyacrylonitrile is dissolved in dimethylformamide and added into premix solution drop by drop, complete spinning solution preparation after stirring and ultrasonic treatment, then the spinning solution is pretreated and added into syringe, and fiber fabric is prepared by electrospinning.The application is designed to have titanium dioxide and silicon dioxide modified, and then added into polyvinylpyrrolidone solution before adding polyacrylonitrile, which realizes the function of uniform dispersion of nanoparticles, solves the problems of nanoparticle agglomeration, interface bonding failure and solvent polarity mismatch, can make nanoparticles uniformly dispersed, eliminates stress concentration point, and improves the interface bonding strength of nanoparticles and matrix.

Description

Technical Field

[0001] This invention relates to the field of textile fabric technology, specifically to a high-strength, wear-resistant nanocomposite fiber fabric and its preparation method. Background Technology

[0002] Early high-performance synthetic fibers such as aramid, while possessing advantages such as high strength, high temperature resistance and light weight, suffered from insufficient interfacial strength with the polymer matrix due to their smooth and inert surface, making it difficult to meet the long-term wear resistance and tear resistance requirements under extreme conditions. In contrast, nanofibers with diameters controlled between 10nm and 100nm have an ultra-high specific surface area that significantly enhances the physical / chemical bonding force between the fiber and the matrix.

[0003] During the preparation of nanocomposite fibers, van der Waals forces between nanoparticles dominate agglomeration, forming micron-sized aggregates, which reduces the effective surface area and active sites. Polar nanofillers are difficult to wet in non-polar polymer matrices, leading to interface defects and reducing fabric performance.

[0004] Patent CN114083877B discloses a nanofiber composite fabric and its production method. The patent achieves the addition of a hydrophilic agent to the electrospinning solution, thereby preparing nanofibers with hydrophilic properties. Sweat can be introduced into the composite fabric, avoiding the defect of traditional nanofiber composite fabrics that cannot pass through sweat, and improving wearing comfort.

[0005] The aforementioned patent involves preparing an electrospinning solution containing a hydrophilic agent and using an electrospinning process to form hydrophilic nanofibers on the inner base fabric after adhesive coating through a high-pressure jet. This produces an intermediate fabric with a nanofiber membrane / inner base fabric structure. The intermediate fabric is then laminated with the adhesive outer base fabric to produce a nanofiber composite fabric with an outer base fabric / nanofiber membrane / inner base fabric composite structure. This improves wearing comfort and allows for optimization in the uniformity of nanofiller dispersion.

[0006] Therefore, this application proposes a high-strength, wear-resistant nanocomposite fiber fabric with uniformly dispersed nanofillers and its preparation method. Summary of the Invention

[0007] The purpose of this invention is to provide a high-strength, wear-resistant nanocomposite fiber fabric and its preparation method, so as to solve the technical problem mentioned in the background art that the easy agglomeration of nanoparticles affects the fabric performance.

[0008] To achieve the above objectives, the present invention provides the following technical solution: a method for preparing a high-strength, wear-resistant nanocomposite fiber fabric, wherein the preparation method is as follows:

[0009] S1: Prepare silicon dioxide and titanium dioxide, dry the silicon dioxide and titanium dioxide and then modify them to obtain modified silicon dioxide and modified titanium dioxide.

[0010] S2: Dissolve the pretreated polyvinylpyrrolidone in a mixed solution of deionized water and dimethylformamide with a volume ratio of 7:3, and stir magnetically for 6 hours in a constant temperature environment of 50℃~60℃.

[0011] S3: Modified silica and modified titanium dioxide are added to a polyvinylpyrrolidone solution and dispersed by ultrasonication to obtain a premixed solution;

[0012] S4: Polyacrylonitrile dissolved in dimethylformamide is added dropwise to the premixed solution, and the spinning solution is prepared by stirring and ultrasonic treatment.

[0013] S5: After pretreatment of the spinning solution, add it to the syringe and use electrospinning to prepare the fiber fabric.

[0014] Preferably, S1 specifically comprises:

[0015] S11: After drying silicon dioxide in a vacuum environment at 105℃ for 6 hours, add a mixed solvent of ethanol and acetic acid with a volume ratio of 4:1 and sonicate for 10 minutes to obtain mixed solution A. After drying titanium dioxide in a vacuum environment at 120℃ for 4 hours, add a dilute nitric acid solution with pH=3 and sonicate for 30 minutes to obtain mixed solution B.

[0016] S12: Add ethanol solution and acetic acid solution to silane coupling agent in sequence, adjust pH to 4.5-5.5, stir and hydrolyze for 30 min at room temperature, then add to mixed solution A, stir at 300 rpm-500 rpm and react at 60℃ for 6 h, centrifuge at 8000 rpm for 10 min, wash with ethanol and deionized water three times in sequence, and dry in vacuum at 60℃ for 12 h to obtain modified silica;

[0017] S13: Add aluminum sulfate solution to mixed solution B, control the temperature at 70℃, add ammonia dropwise until pH=7~8, add the product to a centrifuge, centrifuge at 10000rpm for 15min, rinse with deionized water until neutral to obtain modified titanium dioxide, and store the prepared modified titanium dioxide in 95% ethanol at a temperature of 2℃~8℃.

[0018] Preferably, the concentration of the polyvinylpyrrolidone solution in S2 is 6% to 10%, and the magnetic stirring is carried out at a speed of 200 rpm for 1 to 2 hours, and then the speed is increased to 300 to 400 rpm for 4 to 5 hours.

[0019] Preferably, S3 specifically includes:

[0020] S31: Add 0.5% anionic dispersant to the polyvinylpyrrolidone solution and stir at 800 rpm in a constant temperature environment of 50°C for 10 min.

[0021] S32: Modified titanium dioxide stored in ethanol was slowly injected into the mixture using a constant flow pump at a flow rate of 0.5 mL / min, and the mixture was kept in a water bath at a temperature of 45℃~50℃. The mixture was then sheared at 8000 rpm for 15 min using a high-speed homogenizer, followed by ultrasonic treatment at 40 kHz for 20 min to obtain mixed system A.

[0022] S33: Lower the temperature of mixture A to 35℃~40℃, add ethanol to make the ethanol content in mixture A 70%, and add the modified silica pre-dispersed in ethanol dropwise to mixture A at a rate of 1mL / min.

[0023] S34: Mechanically stir at 300 rpm for 20 min, then ultrasonically stir at 40 kHz for 30 min to obtain a premixed solution.

[0024] Preferably, S4 specifically includes:

[0025] S41: Lower the temperature of the premixed solution to 40℃~45℃, and add dimethylformamide to make the dimethylformamide content of the premixed solution 60%;

[0026] S42: The polyacrylonitrile powder was dried in a vacuum environment at 80°C for 4 hours. Then, the polyacrylonitrile powder was sprinkled into a dimethylformamide solution at 10°C at a rate of 5 g / min and stirred at 200 rpm for 20 min to form a 10% suspension.

[0027] S43: Add the suspension dropwise to the premixed solution at a rate of 1 mL / min, and perform ultrasonic treatment at 40 kHz while stirring at 400 rpm in an environment of 25℃~30℃.

[0028] S44: Raise the temperature to 50°C and continue stirring for 2 hours until the polyacrylonitrile is completely dissolved;

[0029] S45: Raise the temperature to 65℃ and stir at 5000rpm for 10min to obtain the spinning solution.

[0030] Preferably, S5 specifically includes:

[0031] S51: The spinning solution is pretreated by ultrasonic vibration for 20 min, and then the spinning solution is injected into a syringe. The syringe pushes the spinning solution into an electric field with an ambient humidity of 30% and an initial voltage of 18kV at a rate of 0.2mL / h to 0.5mL / h.

[0032] S52: Increase the electric field voltage to 20kV~25kV at a rate of 1kV / 5min;

[0033] S53: Set a roller with a rotation speed of 2000 rpm at a distance of 12cm to 18cm from the syringe to receive the fiber fabric;

[0034] S54: After immersing the fiber fabric in low-temperature water at 5℃~40℃ for cleaning, it is then heat-treated in an environment at 120℃ for 1 hour, and then the temperature is raised to 160℃ for 0.5 hours to obtain the finished fiber fabric.

[0035] Preferably, the mass ratio of polyvinylpyrrolidone, titanium dioxide, silicon dioxide and polyacrylonitrile is 1:0.8:5:10-15.

[0036] Preferably, the concentration of the aluminum sulfate solution added in S13 is 3%.

[0037] Preferably, the anionic dispersant added in S31 is sodium dodecyl sulfate.

[0038] Preferably, the nanocomposite fiber fabric is prepared by the aforementioned preparation method.

[0039] Compared with the prior art, the beneficial effects of the present invention are:

[0040] 1. This invention achieves uniform dispersion of nanoparticles by modifying titanium dioxide and silicon dioxide and adding them sequentially to a polyvinylpyrrolidone solution before adding polyacrylonitrile. This solves the problems of nanoparticle agglomeration, interfacial bonding failure, and solvent polarity mismatch, enabling uniform dispersion of nanoparticles, eliminating stress concentration points, and improving the interfacial bonding strength between nanoparticles and the matrix.

[0041] 2. This invention, by designing and selecting polyvinylpyrrolidone and polyacrylonitrile as two polymers as raw materials, achieves the function of synergistic complementarity of molecular structure, solves the problems of molecular chain slippage, load-bearing capacity collapse, increased brittle fracture and solvent residue defects, and can improve the strength and toughness of finished fabric through the complementary properties of polyvinylpyrrolidone and polyacrylonitrile, improve the load-bearing capacity of finished fabric, reduce the density of microcracks on the surface of finished fabric, and improve the filtration and protective performance of finished fabric.

[0042] 3. This invention, by designing to use deionized water and dimethylformamide as solvents, achieves the function of reducing the use of organic solvents, solving the problems of solvent residue, high cost of organic solvents and great environmental pressure. It can reduce the generation of surface microcracks by the intervention of aqueous phase, improve the performance of finished fiber fabrics and reduce environmental pollution.

[0043] 4. This invention achieves fiber orientation stability by designing a gradient to increase the electric field strength during the electrospinning stage of the spinning solution. It solves the problems of disordered fiber orientation, fiber diameter fluctuation and nanoparticle aggregation. It can suppress phase separation runaway by matching the solvent evaporation rate with segmented voltage, thereby improving the quality of the finished fiber and optimizing the segmented stability of the fiber jet. Attached Figure Description

[0044] Figure 1 This is a schematic diagram of the fiber fabric preparation process of the present invention;

[0045] Figure 2 This is a schematic diagram of the modified titanium dioxide preparation process of the present invention;

[0046] Figure 3 This is a schematic diagram of the modified silica preparation process of the present invention;

[0047] Figure 4 This is a schematic diagram of the premix preparation process of the present invention;

[0048] Figure 5 This is a schematic diagram of the spinning solution preparation process of the present invention;

[0049] Figure 6 This is a schematic diagram of the electrospinning process of the present invention. Detailed Implementation

[0050] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0051] Example 1: Please refer to Figure 1 , Figure 2 , Figure 3 , Figure 4 , Figure 5 and Figure 6 A method for preparing a high-strength, wear-resistant nanocomposite fiber fabric, wherein the preparation method is as follows:

[0052] S1: Prepare silicon dioxide and titanium dioxide, dry the silicon dioxide and titanium dioxide and then modify them to obtain modified silicon dioxide and modified titanium dioxide.

[0053] S2: Dissolve the pretreated polyvinylpyrrolidone in a mixed solution of deionized water and dimethylformamide with a volume ratio of 7:3, and stir magnetically for 6 hours at a constant temperature of 50°C.

[0054] S3: Modified silica and modified titanium dioxide are added to a polyvinylpyrrolidone solution and dispersed by ultrasonication to obtain a premixed solution;

[0055] S4: Polyacrylonitrile dissolved in dimethylformamide is added dropwise to the premixed solution, and the spinning solution is prepared by stirring and ultrasonic treatment.

[0056] S5: After pretreatment of the spinning solution, add it into the syringe and use electrospinning to prepare the fiber fabric.

[0057] Specifically, S1 is:

[0058] S11: After drying silicon dioxide in a vacuum environment at 105℃ for 6 hours, add a mixed solvent of ethanol and acetic acid with a volume ratio of 4:1 and sonicate for 10 minutes to obtain mixed solution A. After drying titanium dioxide in a vacuum environment at 120℃ for 4 hours, add a dilute nitric acid solution with pH=3 and sonicate for 30 minutes to obtain mixed solution B.

[0059] S12: Add ethanol solution and acetic acid solution to silane coupling agent in sequence, adjust pH=5, stir and hydrolyze for 30 min at room temperature, then add to mixed solution A, react at 60℃ for 6 h with stirring at 400 rpm, centrifuge at 8000 rpm for 10 min, wash with ethanol and deionized water 3 times in sequence, and dry in vacuum at 60℃ for 12 h to obtain modified silica;

[0060] S13: Add aluminum sulfate solution to mixed solution B, control the temperature at 70℃, add ammonia dropwise until pH=7, add the product to a centrifuge, centrifuge at 10000rpm for 15min, rinse with deionized water until neutral to obtain modified titanium dioxide, and store the prepared modified titanium dioxide in 95% ethanol at 5℃.

[0061] The concentration of the polyvinylpyrrolidone solution in S2 is 10%, and the magnetic stirring is carried out at a speed of 200 rpm for 2 hours, and then the speed is increased to 400 rpm and stirring is continued for 4 hours.

[0062] Specifically, S3 is:

[0063] S31: Add 0.5% anionic dispersant to the polyvinylpyrrolidone solution and stir at 800 rpm in a constant temperature environment of 50°C for 10 min.

[0064] S32: Modified titanium dioxide stored in ethanol was slowly injected into the mixture using a constant flow pump at a flow rate of 0.5 mL / min, and the mixture was kept in a water bath at 45°C. The mixture was then sheared at 8000 rpm for 15 min using a high-speed homogenizer, followed by ultrasonic treatment at 40 kHz for 20 min to obtain mixed system A.

[0065] S33: Lower the temperature of mixture A to 35℃, add ethanol to make the ethanol content of mixture A 70%, and add the modified silica pre-dispersed in ethanol dropwise to mixture A at a rate of 1mL / min.

[0066] S34: Mechanically stir at 300 rpm for 20 min, then ultrasonically stir at 40 kHz for 30 min to obtain a premixed solution;

[0067] Specifically, S4 is:

[0068] S41: Lower the temperature of the premixed solution to 40°C, and add dimethylformamide to make the dimethylformamide content in the premixed solution 60%;

[0069] S42: The polyacrylonitrile powder was dried in a vacuum environment at 80°C for 4 hours. Then, the polyacrylonitrile powder was sprinkled into a dimethylformamide solution at 10°C at a rate of 5 g / min and stirred at 200 rpm for 20 min to form a 10% suspension.

[0070] S43: Add the suspension dropwise to the premixed solution at a rate of 1 mL / min, and perform ultrasonic treatment at 40 kHz while stirring at 400 rpm in an environment of 25 °C.

[0071] S44: Raise the temperature to 50°C and continue stirring for 2 hours until the polyacrylonitrile is completely dissolved;

[0072] S45: Raise the temperature to 65℃ and stir at 5000rpm for 10min to obtain the spinning solution;

[0073] Specifically, S5 is:

[0074] S51: The spinning solution is pretreated by ultrasonic vibration for 20 min, and then the spinning solution is injected into a syringe. The syringe pushes the spinning solution into an electric field with an ambient humidity of 30% and an initial voltage of 18 kV at a rate of 0.3 mL / h.

[0075] S52: Increase the electric field voltage to 25kV at a rate of 1kV / 5min;

[0076] S53: Set a roller with a rotation speed of 2000 rpm at a distance of 15 cm from the syringe to receive the fibrous fabric.

[0077] S54: After immersing the fiber fabric in low-temperature water at 15°C for cleaning, it is then heat-treated in an environment at 120°C for 1 hour, and then the temperature is raised to 160°C for 0.5 hours to obtain the finished fiber fabric.

[0078] The mass ratio of polyvinylpyrrolidone, titanium dioxide, silicon dioxide and polyacrylonitrile is 1:0.8:5:10;

[0079] The concentration of the aluminum sulfate solution added in S13 is 3%;

[0080] The anionic dispersant added in S31 is sodium dodecyl sulfate;

[0081] Further, sufficient amounts of polyvinylpyrrolidone, titanium dioxide, silicon dioxide, and polyacrylonitrile were prepared according to a mass ratio of 1:0.8:5:10. Polyvinylpyrrolidone was dried in a vacuum environment at 40°C for 24 hours, titanium dioxide at 120°C for 4 hours, silicon dioxide at 105°C for 6 hours, and polyacrylonitrile at 80°C for 4 hours. A mixed solution A was obtained by adding a mixture of ethanol and acetic acid in a volume ratio of 4:1 (3 times the weight of silicon dioxide) to the silicon dioxide, followed by ultrasonic treatment at 28 kHz for 5 minutes and then at 40 kHz for 5 minutes. Ethanol and acetic acid solutions were added to the silane coupling agent to adjust the pH to 5, and the mixture was stirred and hydrolyzed at room temperature for 30 minutes before being added to mixed solution A for silane coupling. The mass ratio of the hydrolysate to mixed solution A was 1:30. The mixture was then stirred at 400 rpm for 6 hours at a constant temperature of 60℃. After the reaction was completed, it was centrifuged at 8000 rpm for 10 minutes. After washing with ethanol and deionized water three times in sequence, it was dried under vacuum at 60℃ for 12 hours to obtain modified silica. Dilute nitric acid solution with pH=3 was added to titanium dioxide and ultrasonically treated for 30 minutes to obtain mixed solution B. A 3% aluminum sulfate solution was added to mixed solution B, and the temperature was controlled at 70℃. Ammonia water was added dropwise until the pH=7. The product was added to a centrifuge and centrifuged at 10000 rpm for 15 minutes. It was then rinsed with deionized water until neutral to obtain modified titanium dioxide. The prepared modified titanium dioxide was stored in 95% ethanol at 5℃.

[0082] The pretreated polyvinylpyrrolidone was dissolved in a mixed solution of deionized water and dimethylformamide with a volume ratio of 7:3. The solution was magnetically stirred at 200 rpm for 2 hours in a constant temperature environment of 50°C. Then the stirring speed was increased to 400 rpm and stirred for another 4 hours to obtain a polyvinylpyrrolidone solution with a concentration of 10%.

[0083] Add 0.5% sodium dodecyl sulfate to a polyvinylpyrrolidone solution and stir at 800 rpm in a constant temperature environment of 50°C for 10 min. Slowly inject modified titanium dioxide stored in ethanol through a constant flow pump at a flow rate of 0.5 mL / min and maintain the temperature at 45°C in a water bath. Shear the mixture at 8000 rpm for 15 min using a high-speed homogenizer, and then sonicate it at 40 kHz for 20 min to obtain mixture A. Lower the temperature of mixture A to 35°C and add ethanol to make the ethanol content of mixture A 70%. Add the modified silica pre-dispersed in ethanol dropwise to mixture A at a rate of 1 mL / min and mechanically stir at 300 rpm for 20 min. Then sonicate it at 40 kHz for 30 min to obtain a premix.

[0084] The temperature of the premix was lowered to 40°C, and dimethylformamide was added to make the dimethylformamide content in the premix 60%. Polyacrylonitrile powder was dried in a vacuum environment at 80°C for 4 hours. Then, the polyacrylonitrile powder was sprinkled into a 10°C dimethylformamide solution at a rate of 5 g / min, and stirred at 200 rpm for 20 minutes to form a 10% suspension. The suspension was added dropwise to the treated premix at a rate of 1 mL / min. The mixture was then sonicated at 40 kHz while stirring at 400 rpm in an environment of 25°C. The temperature was then increased to 50°C, and stirring was continued for 2 hours until the polyacrylonitrile was completely dissolved. Finally, the temperature was increased to 65°C. The spinning solution was obtained by stirring at 5000 rpm for 10 min. The spinning solution was pretreated by ultrasonic vibration for 20 min. Then the spinning solution was injected into a syringe. The syringe pushed the spinning solution into an electric field with an ambient humidity of 30% and an initial voltage of 18 kV at a rate of 0.3 mL / h. The electric field voltage was increased to 25 kV at a rate of 1 kV / 5 min. A roller rotating at 2000 rpm was placed 15 cm away from the syringe to receive the fiber fabric. The fiber fabric was immersed in low temperature water at 15℃ for cleaning and then heat-treated in an environment of 120℃ for 1 h. The temperature was then increased to 160℃ for 0.5 h to obtain the finished fiber fabric.

[0085] Control group 1: The timing of adding modified silica and modified titanium dioxide was changed to mixing polyvinylpyrrolidone and polyacrylonitrile, while other conditions remained unchanged, and fiber fabric was prepared.

[0086] Control group 2: Polyacrylonitrile was removed, and only polyvinylpyrrolidone was used as the matrix, with other conditions unchanged, to prepare fiber fabric;

[0087] Control group 3: Polyvinylpyrrolidone was removed, and only polyacrylonitrile was used as the matrix, with other conditions remaining unchanged, for the preparation of fiber fabrics.

[0088] Control group 4: The solvent for dissolving polyvinylpyrrolidone was replaced with dimethylformamide, and other conditions remained unchanged to prepare the fiber fabric;

[0089] Control group 5: After the spinning solution was prepared, spinning was carried out using a uniform electric field, and other conditions remained unchanged, and fiber fabric was prepared.

[0090] Example 2: Please refer to Figure 2 and Figure 3 A method for preparing a high-strength, wear-resistant nanocomposite fiber fabric, wherein step S1 specifically comprises:

[0091] S11: After drying silicon dioxide in a vacuum environment at 105℃ for 6 hours, add a mixed solvent of ethanol and acetic acid with a volume ratio of 4:1 and sonicate for 10 minutes to obtain mixed solution A. After drying titanium dioxide in a vacuum environment at 120℃ for 4 hours, add a dilute nitric acid solution with pH=3 and sonicate for 30 minutes to obtain mixed solution B.

[0092] S12: Add ethanol solution and acetic acid solution to silane coupling agent in sequence, adjust pH=5, stir and hydrolyze for 30 min at room temperature, then add to mixed solution A, react at 60℃ for 6 h with stirring at 400 rpm, centrifuge at 8000 rpm for 10 min, wash with ethanol and deionized water 3 times in sequence, and dry in vacuum at 60℃ for 12 h to obtain modified silica;

[0093] S13: Add aluminum sulfate solution to mixed solution B, control the temperature at 70℃, add ammonia dropwise until pH=7, add the product to a centrifuge, centrifuge at 10000rpm for 15min, rinse with deionized water until neutral to obtain modified titanium dioxide, and store the prepared modified titanium dioxide in 95% ethanol at 5℃.

[0094] Furthermore, by increasing the drying temperature and extending the drying time of silica and titanium dioxide, adsorbed water within the silica and titanium dioxide is removed more thoroughly. The silane coupling agent is hydrolyzed at room temperature to form a silane hydrolysate, which then forms a silanol. Subsequently, the temperature is increased to 60°C for a grafting reaction. The silanol condenses with hydroxyl groups on the silica surface to form covalent bonds, constructing a dense Si-O-Si network on the silica surface. This introduces condensation groups into the particle surface, reducing the surface energy of silica and enhancing its compatibility with dimethylformamide. It also avoids the silica agglomeration phenomenon that occurs with direct addition. During the modification of titanium dioxide, aluminum ions on the titanium dioxide surface... The surface hydrolysis produces alternating layers of aluminum hydroxide, which, after drying, are converted into an alumina coating layer. This coating shields the photocatalytic activity of titanium dioxide, preventing UV degradation of the polymer chains. Simultaneously, it neutralizes the surface acidic sites resulting from nitric acid treatment, reducing charge repulsion between titanium dioxide and polyvinylpyrrolidone amide groups. The alumina coating on the modified titanium dioxide surface prevents dissolution after the addition of polyacrylonitrile. The hydrophobicity of the modified silica is compatible with dimethylformamide, preventing precipitation in a mixed solution of deionized water and dimethylformamide. Furthermore, the addition of modified titanium dioxide improves the storage stability of the spinning solution, extending its shelf life.

[0095] Example 3: Please refer to Figure 1 , Figure 4 and Figure 5 A method for preparing a high-strength, wear-resistant nanocomposite fiber fabric, wherein the preparation method is as follows:

[0096] S1: Prepare silicon dioxide and titanium dioxide, dry the silicon dioxide and titanium dioxide and then modify them to obtain modified silicon dioxide and modified titanium dioxide.

[0097] S2: Dissolve the pretreated polyvinylpyrrolidone in a mixed solution of deionized water and dimethylformamide with a volume ratio of 7:3, and stir magnetically for 6 hours at a constant temperature of 50°C.

[0098] S3: Modified silica and modified titanium dioxide are added to a polyvinylpyrrolidone solution and dispersed by ultrasonication to obtain a premixed solution;

[0099] S4: Polyacrylonitrile dissolved in dimethylformamide is added dropwise to the premixed solution, and the spinning solution is prepared by stirring and ultrasonic treatment.

[0100] S5: After pretreatment of the spinning solution, add it into the syringe and use electrospinning to prepare the fiber fabric.

[0101] Specifically, S3 is:

[0102] S31: Add 0.5% anionic dispersant to the polyvinylpyrrolidone solution and stir at 800 rpm in a constant temperature environment of 50°C for 10 min.

[0103] S32: Modified titanium dioxide stored in ethanol was slowly injected into the mixture using a constant flow pump at a flow rate of 0.5 mL / min, and the mixture was kept in a water bath at 45°C. The mixture was then sheared at 8000 rpm for 15 min using a high-speed homogenizer, followed by ultrasonic treatment at 40 kHz for 20 min to obtain mixed system A.

[0104] S33: Lower the temperature of mixture A to 35℃, add ethanol to make the ethanol content of mixture A 70%, and add the modified silica pre-dispersed in ethanol dropwise to mixture A at a rate of 1mL / min.

[0105] S34: Mechanically stir at 300 rpm for 20 min, then ultrasonically stir at 40 kHz for 30 min to obtain a premixed solution;

[0106] Specifically, S4 is:

[0107] S41: Lower the temperature of the premixed solution to 40°C, and add dimethylformamide to make the dimethylformamide content in the premixed solution 60%;

[0108] S42: The polyacrylonitrile powder was dried in a vacuum environment at 80°C for 4 hours. Then, the polyacrylonitrile powder was sprinkled into a dimethylformamide solution at 10°C at a rate of 5 g / min and stirred at 200 rpm for 20 min to form a 10% suspension.

[0109] S43: Add the suspension dropwise to the premixed solution at a rate of 1 mL / min, and perform ultrasonic treatment at 40 kHz while stirring at 400 rpm in an environment of 25 °C.

[0110] S44: Raise the temperature to 50°C and continue stirring for 2 hours until the polyacrylonitrile is completely dissolved;

[0111] S45: Raise the temperature to 65℃ and stir at 5000rpm for 10min to obtain the spinning solution;

[0112] The anionic dispersant added in S31 is sodium dodecyl sulfate;

[0113] Furthermore, by selecting silica and titanium dioxide as nanofillers, after modifying the silica and titanium dioxide, 5% sodium dodecyl sulfate was added to the polyvinylpyrrolidone solution as a dispersant to establish an electrostatic repulsion barrier, preferentially occupying the active sites of polyvinylpyrrolidone and reserving binding sites for the nanofillers. Then, modified titanium dioxide stored in ethanol was slowly injected at a flow rate of 0.5 mL / min. A 45℃ water bath and 8000 rpm high-speed shearing were used to reduce the local concentration gradient of the modified titanium dioxide, promoting the intercalation of polyvinylpyrrolidone molecular chains through shearing. Subsequently, the temperature was lowered to reduce the molecular chain movement rate and avoid flocculation. After the addition of ethanol, the 70% sodium dodecyl sulfate solution... The high ethanol environment weakens the hydrophilicity of polyvinylpyrrolidone, thus adapting it to modified silica. Simultaneously, it avoids competitive adsorption and interfacial defects caused by the simultaneous addition of modified titanium dioxide and modified silica. Subsequently, polyacrylonitrile dissolved in dimethylformamide is added dropwise to the premix at 1 mL / min, followed by a three-stage heating process to obtain the spinning solution. By using polyvinylpyrrolidone and polyacrylonitrile as the matrix, the cross-linking of pyrrolidone groups with cyano groups enhances interfacial compatibility and inhibits phase separation. Polyvinylpyrrolidone occupies the cyano reaction sites of polyacrylonitrile, delaying the aging of the finished fiber fabric. Furthermore, polyvinylpyrrolidone blocks intermolecular cross-linking of polyacrylonitrile, promoting intramolecular stability.

[0114] Example 4: Please refer to Figure 1 A method for preparing this high-strength, wear-resistant nanocomposite fiber fabric, wherein the preparation method comprises:

[0115] S1: Prepare silicon dioxide and titanium dioxide, dry the silicon dioxide and titanium dioxide and then modify them to obtain modified silicon dioxide and modified titanium dioxide.

[0116] S2: Dissolve the pretreated polyvinylpyrrolidone in a mixed solution of deionized water and dimethylformamide with a volume ratio of 7:3, and stir magnetically for 6 hours at a constant temperature of 50°C.

[0117] S3: Modified silica and modified titanium dioxide are added to a polyvinylpyrrolidone solution and dispersed by ultrasonication to obtain a premixed solution;

[0118] S4: Polyacrylonitrile dissolved in dimethylformamide is added dropwise to the premixed solution, and the spinning solution is prepared by stirring and ultrasonic treatment.

[0119] S5: After pretreatment of the spinning solution, add it into the syringe and use electrospinning to prepare the fiber fabric.

[0120] The concentration of the polyvinylpyrrolidone solution in S2 is 10%, and the magnetic stirring is carried out at a speed of 200 rpm for 2 hours, and then the speed is increased to 400 rpm and stirring is continued for 4 hours.

[0121] Furthermore, when dissolving polyvinylpyrrolidone (PVP), a mixed solution of deionized water and dimethylformamide with a volume ratio of 7:3 was selected as the solvent. PVP molecular chains contain amide groups, which readily form intermolecular or intramolecular hydrogen bond networks. Upon addition of deionized water, the strong hydrogen bond competition breaks the PPVP's own hydrogen bonds. The carbonyl and dimethylamino groups of dimethylformamide further induce dipole-dipole interactions in the PPVP ring, promoting molecular chain deentanglement and improving the dissolution efficiency of PPVP. Water molecules form a primary solvation layer in the hydrophilic region of PPVP, weakening the solubility of water molecules. Inter-polymer chain forces allow dimethylformamide to penetrate the hydrophobic region of polyvinylpyrrolidone (PVP). Van der Waals forces disperse the hydrophobic segments, forming a secondary solvation layer. Using a 7:3 volume ratio of deionized water and dimethylformamide as a solvent reduces the amount of dimethylformamide used, avoiding environmental pollution and increased processing difficulties associated with large amounts of organic solvents. Simultaneously, the deionized water and dimethylformamide mixture lowers the concentration of the PPVP solution after dissolving PPVP, preventing clogging during electrospinning, improving spinning continuity, and resulting in a more uniform fiber diameter distribution.

[0122] Example 5: Please refer to Figure 6 A method for preparing a high-strength, wear-resistant nanocomposite fiber fabric, wherein step S5 specifically comprises:

[0123] S51: The spinning solution is pretreated by ultrasonic vibration for 20 min, and then the spinning solution is injected into a syringe. The syringe pushes the spinning solution into an electric field with an ambient humidity of 30% and an initial voltage of 18 kV at a rate of 0.3 mL / h.

[0124] S52: Increase the electric field voltage to 25kV at a rate of 1kV / 5min;

[0125] S53: Set a roller with a rotation speed of 2000 rpm at a distance of 15 cm from the syringe to receive the fibrous fabric.

[0126] S54: After immersing the fiber fabric in low-temperature water at 15°C for cleaning, it is then heat-treated in an environment at 120°C for 1 hour, and then the temperature is raised to 160°C for 0.5 hours to obtain the finished fiber fabric.

[0127] Furthermore, the solvent used to dissolve polyvinylpyrrolidone was a mixture of deionized water and dimethylformamide in a volume ratio of 7:3, which contained water molecules. During electrospinning of the prepared spinning solution, the electric field voltage intensity needed to be strictly controlled to avoid instability in the spinning solution jet caused by water molecules. After removing air bubbles from the spinning solution by ultrasonic vibration, the spinning solution was injected into a syringe and pushed into an electric field with an ambient humidity of 30% and an initial voltage intensity of 18kV at a rate of 0.3mL / h. This allowed the spinning solution to form a stable Taylor cone, preventing jet sputtering. Subsequently, the voltage was increased to 1kV / 5min. The rate of n increases the voltage intensity of the electric field to 25kV, reducing the fiber diameter variation coefficient and making the formed fiber diameter more stable and consistent. In addition, by reducing the electric field humidity to 30%, the focusing effect of the electric field on the jet is enhanced through a low-humidity environment, accelerating the evaporation of the solvent gradient and suppressing the formation of liquid droplets. After the roller with a shortened collection distance completes the collection of the fiber fabric, the residual charge on the fiber fabric is removed by low-temperature water washing to avoid the adsorption phenomenon between the fiber fabrics due to static electricity. Subsequently, gradient heat treatment is used to reorganize the orientation of the molecular chain of the fiber fabric, avoiding excessive stretching of the molecular chain caused by the high electric field, thus improving the quality of the finished fiber fabric.

[0128] Performance testing

[0129] Test 1: Ten samples of fiber fabrics prepared in Example 1 and Control Groups 1-5 were prepared, each measuring 40cm*40cm. The selected fiber fabric samples were tested according to GB / T21196.1-2007 "Textiles - Martindale Method: Determination of Plant Abrasion Resistance - Part 1: Martindale Abrasion Tester". The test results are shown in Table 1.

[0130] Table 1. Abrasion Resistance Test Results of Fiber Fabrics

[0131] Abrasion resistance revolutions (r) Example 1 42500 Control group 1 31800 Control group 2 18600 Control group 3 12400 Control group 4 26300 Control group 5 29700

[0132] As shown in Table 1, the abrasion resistance of the fiber fabric prepared in Example 1 is significantly better than that of the control groups 1-5. A comparison between Example 1 and control group 1 shows that Example 1, by sequentially adding modified titanium dioxide and modified silica to a polyvinylpyrrolidone solution followed by the addition of polyacrylonitrile dissolved in dimethylformamide, avoids competitive adsorption between nanoparticles and reduces stress concentration caused by agglomeration. A comparison between Example 1 and control groups 2 and 3 shows that the composite matrix system of polyvinylpyrrolidone and polyacrylonitrile can compensate for the rigidity of polyacrylonitrile through the flexibility of polyvinylpyrrolidone. A comparison between Example 1 and control group 4 shows that using only dimethylformamide as a solvent causes excessive shrinkage of polyvinylpyrrolidone, thereby weakening the interfacial bonding force of the nanoparticles. A comparison between Example 1 and control group 5 shows that a uniform electric field leads to jet whipping, resulting in disordered fiber arrangement.

[0133] Test 2: Ten samples of fiber fabrics prepared in Example 1 and Control Groups 1-5 were prepared, each measuring 40cm*40cm. The tensile properties of the fiber fabric samples were tested according to the test methods in GB / T3923.1-1997 "Textiles - Determination of Tensile Properties, Breaking Strength and Elongation at Break - Strip Method". The test results are shown in Table 2.

[0134] Table 2. Results of Tensile Properties Test of Fiber Fabrics

[0135] Fracture strength (N) Elongation at break (%) Example 1 86.1 28.7 Control group 1 71.6 22.5 Control group 2 49.2 35.1 Control group 3 63.4 12.8 Control group 4 69.5 21.7 Control group 5 76.1 26.8

[0136] As shown in Table 2, the tensile properties of the fiber fabric prepared in Example 1 are better than those of the fiber fabrics prepared in Control Groups 1-5. A comparison between Example 1 and Control Group 1 shows that the addition of nanoparticles leads to agglomeration, causing stress concentration and resulting in early fracture. A comparison between Example 1 and Control Groups 2 and 3 shows that using only polyvinylpyrrolidone as the matrix results in the lack of polyacrylonitrile, leading to molecular chain slippage. Although this increases the elongation at break, it causes a sharp drop in breaking strength. Using only polyacrylonitrile results in the lack of polyvinylpyrrolidone, leading to high brittleness of the finished fiber fabric. The alumina coating layer of modified silica does not bond sufficiently with polyacrylonitrile. A comparison between Example 1 and Control Group 3 shows that using only dimethylformamide as a solvent causes polyvinylpyrrolidone to shrink, reducing the nanoparticle encapsulation rate. A comparison between Example 1 and Control Group 5 shows that spinning using a gradient electric field optimizes fiber orientation and avoids uneven load distribution.

[0137] Working principle: Prepare sufficient amounts of polyvinylpyrrolidone, titanium dioxide, silicon dioxide, and polyacrylonitrile in a mass ratio of 1:0.8:5:10. Dry the polyvinylpyrrolidone in a vacuum environment at 40℃ for 24 hours, the titanium dioxide at 120℃ for 4 hours, the silicon dioxide at 105℃ for 6 hours, and the polyacrylonitrile at 80℃ for 4 hours. Add a mixture of ethanol and acetic acid (volume ratio 4:1, 3 times the weight of silicon dioxide) to the silicon dioxide. After ultrasonic treatment at 28kHz for 5 minutes, followed by ultrasonic treatment at 40kHz for 5 minutes, obtain mixed solution A. Adjust the pH to 4.5–5.5 by adding ethanol and acetic acid solutions to the silane coupling agent and stirring for 30 minutes at room temperature. Then add this mixture to mixed solution A. The mass ratio of the hydrolysate to mixed solution A was 1:30. The mixture was then stirred at 400 rpm for 6 hours at a constant temperature of 60℃. After the reaction was completed, the mixture was centrifuged at 8000 rpm for 10 minutes. After washing with ethanol and deionized water three times in sequence, the mixture was dried under vacuum at 60℃ for 12 hours to obtain modified silica. Dilute nitric acid solution with pH=3 was added to titanium dioxide and ultrasonically treated for 30 minutes to obtain mixed solution B. A 3% aluminum sulfate solution was added to mixed solution B, and the temperature was controlled at 70℃. Ammonia water was added dropwise until the pH reached 7-8. The product was added to a centrifuge and centrifuged at 10000 rpm for 15 minutes. The mixture was washed with deionized water until neutral to obtain modified titanium dioxide. The prepared modified titanium dioxide was stored in 95% ethanol at a temperature of 2℃-8℃.

[0138] The pretreated polyvinylpyrrolidone was dissolved in a mixed solution of deionized water and dimethylformamide at a volume ratio of 7:3. The mixture was magnetically stirred at 200 rpm for 1 to 2 hours in a constant temperature environment of 50℃ to 60℃. Then the stirring speed was increased to 300 rpm to 400 rpm and stirred for another 4 to 5 hours to obtain a polyvinylpyrrolidone solution with a concentration of 6% to 10%.

[0139] Add 0.5% sodium dodecyl sulfate to a polyvinylpyrrolidone solution and stir at 800 rpm in a constant temperature environment of 50°C for 10 min. Slowly inject modified titanium dioxide stored in ethanol through a constant flow pump at a flow rate of 0.5 mL / min, and maintain a water bath temperature of 45°C to 50°C. Shear the mixture at 8000 rpm for 15 min using a high-speed homogenizer, and then sonicate it at 40 kHz for 20 min to obtain mixture A. Lower the temperature of mixture A to 35°C to 40°C, add ethanol to make the ethanol content of mixture A 70%, and add the modified silica pre-dispersed in ethanol dropwise to mixture A at a rate of 1 mL / min. Mechanically stir at 300 rpm for 20 min, and then sonicate it at 40 kHz for 30 min to obtain a premix.

[0140] The temperature of the premix was lowered to 40℃~45℃, and dimethylformamide was added to make the dimethylformamide content in the premix 60%. Polyacrylonitrile powder was dried in a vacuum environment at 80℃ for 4 hours. Then, the polyacrylonitrile powder was sprinkled into a 10℃ dimethylformamide solution at a rate of 5 g / min and stirred at 200 rpm for 20 min to form a 10% suspension. The suspension was added dropwise to the premix at a rate of 1 mL / min and subjected to ultrasonic treatment at 40 kHz while stirring at 400 rpm in an environment of 25℃~30℃. The temperature was gradually increased to 50℃ and 65℃. After stirring, the spinning solution was obtained. The spinning solution was pretreated with ultrasonic vibration for 20 minutes, and then injected into a syringe. The syringe pushed the spinning solution into an electric field with an ambient humidity of 30% and an initial voltage of 18kV at a rate of 0.2mL / h to 0.5mL / h. The electric field voltage was increased to 20kV to 25kV at a rate of 1kV / 5min. A roller rotating at 2000rpm was placed 12cm to 18cm away from the syringe to receive the fiber fabric. The fiber fabric was washed by immersing it in low-temperature water at 5℃ to 40℃, and then heat-treated in an environment of 120℃ for 1 hour. The temperature was then increased to 160℃ for 0.5 hours to obtain the finished fiber fabric.

[0141] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit or essential characteristics. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, all variations falling within the meaning and scope of equivalents of the claims are intended to be included within the present invention. No reference numerals in the claims should be construed as limiting the scope of the claims.

Claims

1. A method for preparing a high-strength, wear-resistant nanocomposite fiber fabric, characterized in that: The preparation method is as follows: S1: Prepare silicon dioxide and titanium dioxide, dry the silicon dioxide and titanium dioxide and then modify them to obtain modified silicon dioxide and modified titanium dioxide. S2 Dissolves the dried polyvinylpyrrolidone in a mixed solution of deionized water and dimethylformamide at a volume ratio of 7:3, and stirs it magnetically for 6 hours in a constant temperature environment of 50℃~60℃. S3: Modified silica and modified titanium dioxide are added to a polyvinylpyrrolidone solution and dispersed by ultrasonication to obtain a premixed solution; S4: Polyacrylonitrile dissolved in dimethylformamide is added dropwise to the premixed solution, and the spinning solution is prepared by stirring and ultrasonic treatment. S5: After pretreatment of the spinning solution, add it into the syringe and use electrospinning to prepare the fiber fabric. Specifically, S3 is: S31: Add 0.5% anionic dispersant to the polyvinylpyrrolidone solution and stir at 800 rpm in a constant temperature environment of 50°C for 10 min. S32: Modified titanium dioxide stored in ethanol was slowly injected into the mixture using a constant flow pump at a flow rate of 0.5 mL / min, and the mixture was kept in a water bath at a temperature of 45℃~50℃. The mixture was then sheared at 8000 rpm for 15 min using a high-speed homogenizer, followed by ultrasonic treatment at 40 kHz for 20 min to obtain mixed system A. S33: Lower the temperature of mixture A to 35℃~40℃, add ethanol to make the ethanol content in mixture A 70%, and add the modified silica pre-dispersed in ethanol dropwise to mixture A at a rate of 1mL / min. S34: Mechanically stir at 300 rpm for 20 min, then ultrasonically stir at 40 kHz for 30 min to obtain a premixed solution.

2. The method for preparing a high-strength, wear-resistant nanocomposite fiber fabric according to claim 1, characterized in that: Specifically, S1 is: S11: After drying silicon dioxide in a vacuum environment at 105℃ for 6 hours, add a mixed solvent of ethanol and acetic acid with a volume ratio of 4:1 and sonicate for 10 minutes to obtain mixed solution A. After drying titanium dioxide in a vacuum environment at 120℃ for 4 hours, add a dilute nitric acid solution with pH=3 and sonicate for 30 minutes to obtain mixed solution B. S12: Add ethanol solution and acetic acid solution to silane coupling agent in sequence, adjust pH to 4.5-5.5, stir and hydrolyze for 30 min at room temperature, then add to mixed solution A, stir at 300 rpm-500 rpm and react at 60℃ for 6 h, centrifuge at 8000 rpm for 10 min, wash with ethanol and deionized water three times in sequence, and dry in vacuum at 60℃ for 12 h to obtain modified silica; S13: Add aluminum sulfate solution to mixed solution B, control the temperature at 70℃, add ammonia dropwise until pH=7~8, add the product to a centrifuge, centrifuge at 10000rpm for 15min, rinse with deionized water until neutral to obtain modified titanium dioxide, and store the prepared modified titanium dioxide in 95% ethanol at a temperature of 2℃~8℃.

3. The method for preparing a high-strength, wear-resistant nanocomposite fiber fabric according to claim 1, characterized in that: The concentration of the polyvinylpyrrolidone solution in S2 is 6% to 10%, and the magnetic stirring is carried out at a speed of 200 rpm for 1 to 2 hours, and then the speed is increased to 300 to 400 rpm and stirring is continued for 4 to 5 hours.

4. The method for preparing a high-strength, wear-resistant nanocomposite fiber fabric according to claim 1, characterized in that: Specifically, S4 is: S41: Lower the temperature of the premixed solution to 40℃~45℃, and add dimethylformamide to make the dimethylformamide content of the premixed solution 60%; S42: The polyacrylonitrile powder was dried in a vacuum environment at 80°C for 4 hours. Then, the polyacrylonitrile powder was sprinkled into a dimethylformamide solution at 10°C at a rate of 5 g / min and stirred at 200 rpm for 20 min to form a 10% suspension. S43: Add the suspension dropwise to the premixed solution at a rate of 1 mL / min, and perform ultrasonic treatment at 40 kHz while stirring at 400 rpm in an environment of 25℃~30℃. S44: Raise the temperature to 50°C and continue stirring for 2 hours until the polyacrylonitrile is completely dissolved; S45: Raise the temperature to 65℃ and stir at 5000rpm for 10min to obtain the spinning solution.

5. The method for preparing a high-strength, wear-resistant nanocomposite fiber fabric according to claim 1, characterized in that: Specifically, S5 is: S51: The spinning solution is pretreated by ultrasonic vibration for 20 min, and then the spinning solution is injected into a syringe. The syringe pushes the spinning solution into an electric field with an ambient humidity of 30% and an initial voltage of 18kV at a rate of 0.2mL / h to 0.5mL / h. S52: Increase the electric field voltage to 20kV~25kV at a rate of 1kV / 5min; S53: Set a roller with a rotation speed of 2000 rpm at a distance of 12cm to 18cm from the syringe to receive the fiber fabric; S54: After immersing the fiber fabric in low-temperature water at 5℃~40℃ for cleaning, it is then heat-treated in an environment at 120℃ for 1 hour, and then the temperature is raised to 160℃ for 0.5 hours to obtain the finished fiber fabric.

6. The method for preparing a high-strength, wear-resistant nanocomposite fiber fabric according to claim 1, characterized in that: The mass ratio of polyvinylpyrrolidone, titanium dioxide, silicon dioxide and polyacrylonitrile is 1:0.8:5:10-15.

7. The method for preparing a high-strength, wear-resistant nanocomposite fiber fabric according to claim 2, characterized in that: The concentration of the aluminum sulfate solution added in S13 is 3%.

8. The method for preparing a high-strength, wear-resistant nanocomposite fiber fabric according to claim 1, characterized in that: The anionic dispersant added in S31 is sodium dodecyl sulfate.

9. A high-strength, wear-resistant nanocomposite fiber fabric, applicable to the preparation method of the high-strength, wear-resistant nanocomposite fiber fabric according to any one of claims 1-8, characterized in that: The nanocomposite fiber fabric is prepared by the aforementioned preparation method.

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