Plied yarn and twisting process thereof

Abstract

The invention relates to the technical field of twisted yarns, in particular to a twisted yarn and a twisting process thereof, and the twisted yarn comprises the following components: polyester fibers, silver nanowires, spider silk-like protein, silicon dioxide aerogel, nylon 66, carbon fiber membrane TPU, an antioxidant, an ultraviolet stabilizer and a lubricant. The performance of the stranded yarn is improved by introducing a novel material and an advanced preparation technology. The introduction of the nanometer material brings new possibility for improving the performance of the stranded yarn. Due to the unique size effect and surface effect of the nano material, the mechanical property, thermal stability and functionality of the composite material can be remarkably improved.

Description

Technical Field

[0001] The invention relates to the technical field of twisted yarns, in particular to a twisted yarn and a twisting process thereof. Background Art

[0002] With the continuous progress of materials science, fiber materials are increasingly used in various fields, especially in textiles, aerospace, military and other fields. Although traditional fiber materials have certain strength and durability, they are often difficult to meet the growing performance requirements in the face of complex and changing use environments. Therefore, the research and development of new fiber materials with excellent comprehensive performance has become one of the hot topics in the current field of materials science.

[0003] As a high-performance fiber material, the performance of twisted yarn directly affects the quality and service life of the product. Although the traditional twisted yarn preparation process is mature, it has many shortcomings when facing higher performance requirements.

[0004] Deficiencies in the existing technology:

[0005] Performance balance problem: Existing twisted yarns often sacrifice toughness and other key properties while pursuing high strength. How to improve toughness and durability while maintaining high strength is a major challenge facing current technology.

[0006] Insufficient environmental adaptability: When facing extreme environments (such as high temperature, low temperature, ultraviolet radiation, etc.), the performance of traditional twisted yarns is easily affected, and they may even degrade or fail.

[0007] Single functionality: Most existing twisted yarns only have basic mechanical properties and lack multifunctionality, such as special properties such as antibacterial, antistatic, and self-cleaning, which limits the further expansion of their application scope.

[0008] Therefore, we propose a plied yarn and a twisting process thereof to solve the above problems. Summary of the invention

[0009] The purpose of the present invention is to solve the shortcomings of the prior art and to propose a twisted yarn and a twisting process thereof.

[0010] In order to achieve the above object, the present invention adopts the following technical solutions:

[0011] A twisted yarn comprises the following components in parts by weight: 25-35 parts of polyester fiber, 3-7 parts of nano silver wire, 10-20 parts of spider silk protein, 3-7 parts of silica aerogel, 15-25 parts of nylon 661, 5-15 parts of carbon fiber film TPU, 1-3 parts of antioxidant, 1-3 parts of ultraviolet stabilizer and 0.5-1.5 parts of lubricant.

[0012] As the preferred technical solution:

[0013] The twisted yarn as described above comprises the following components in parts by weight: 28 parts of polyester fiber, 4 parts of nano silver wire, 13 parts of spider silk protein, 4 parts of silica aerogel, 18 parts of nylon 66, 7 parts of carbon fiber film TPU, 2 parts of antioxidant, 2 parts of ultraviolet stabilizer, and 0.9 parts of lubricant.

[0014] The twisted silk as described above, wherein the diameter of the polyester fiber is controlled at 10-20 microns, and the crystallinity of the polyester fiber is 60%-100%; the particle size of the nano silver wire is 25-50 nanometers, and the aspect ratio is 100-450; the amino acid sequence of the spider silk protein has a similarity of 80%-100% with the key sequence of the natural spider silk protein, and the content of the β-folded structure in the secondary structure of the spider silk protein accounts for 60%-90% of the total protein structure; the porosity of the silica aerogel is 90%-100%, and the particle size of the silica particles constituting the aerogel is 10-50 nanometers; the crystallinity of the nylon 66 is 5 0%-80%, the molecular weight of nylon 66 is 20,000-30,000 Daltons; the diameter of the carbon fiber in the carbon fiber film TPU is 5-10 microns, and the content of the carbon fiber in the film is 30%-70%; the antioxidant is one of tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester and dibutylhydroxytoluene, the ultraviolet stabilizer is one of 2-(2'-hydroxy-5'-methylphenyl)benzotriazole and 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, and the lubricant is one of long-chain fatty acid esters or silicone oil compounds.

[0015] In the above-mentioned twisted silk, the polyester fiber is introduced with functional groups through chemical modification, and the functional groups include hydrophilic groups or antistatic groups; the nano silver wires are arranged linearly in the twisted silk, and hydrogen bonds or chemical bonds are formed between the nano silver wires and other components through surface modification, thereby enhancing the interface interaction and overall stability; the molecular chains of the spider silk-like protein form a structure of three rows parallel to each other, simulating the multi-level structure of natural spider silk, and the spider silk-like protein and other polymer components form an interpenetrating network through the interpenetrating network technology, thereby enhancing the composite properties of the twisted silk, and assuming that the composite properties of the twisted silk are P_c, then:

[0016] P_c=k_2\cdotD^{n_2};

[0017] Wherein, D is the density of the interpenetrating network, indicating the degree of interweaving between the spider silk protein and other polymer components; k_2 is a constant related to the material composition and processing conditions; n_2 is an index of the influence of the density of the interpenetrating network on the composite performance; during the formation of the silica aerogel, a primary pre-network and a secondary pre-network structure are constructed to optimize its pore structure and thermal insulation performance; nylon 66 is copolymerized and modified to introduce a third monomer with a toughening function.

[0018] A twisted yarn as described above, wherein the polyester fiber has a supramolecular self-assembly structure, and an ordered nanoscale domain is formed inside the fiber, thereby enhancing its mechanical properties and heat resistance. By controlling the stereochemistry during the polymerization process, the molecular chain of the polyester fiber presents a helical conformation to improve its elasticity and resilience. The nano silver wire is constructed with a core-shell structure, wherein the core is pure silver and the shell is a protective layer. By controlling the arrangement and connection of the nano silver wires, a multi-dimensional conductive network is formed to achieve more efficient current transmission. The spider silk-like protein self-assembles into a nanoscale fiber array to simulate the fine structure of natural spider silk. Groups that can form dynamic cross-linking domains are introduced into the spider silk-like protein. These cross-linking domains can be reversibly formed and broken under stress, thereby dissipating energy and improving the impact resistance of the material. The carbon fiber film TPU has a stacked composite structure, wherein the carbon fiber layer provides strength, and the TPU layer provides flexibility and impact resistance.

[0019] A second aspect of the present invention provides a twisting process for a plied yarn, comprising the following steps:

[0020] S1: Using the co-spinning technology, polyester fiber and nylon 66 are mixed in a molten state and added into a twin-screw extruder. After high-temperature melting, mixing, and extrusion, a continuous base fiber layer is formed through a spinneret.

[0021] S2: Using ultrasonic dispersion technology to disperse the silver nanowires, breaking the agglomeration of the silver nanowires, slowly adding the dispersed silver nanowires into the base fiber layer, and adding lubricants to obtain mixed fibers;

[0022] S3: evenly coating the dissolved spider silk protein solution on the mixed fiber, and using a coating device to ensure that each fiber is evenly coated;

[0023] S4: Add silica aerogel to the fibers coated with spider silk protein, and use the porous structure of aerogel to enhance the thermal insulation performance of the twisted silk;

[0024] S5: placing the carbon fiber film TPU in a mold of a hot press, heating it to above the melting point of TPU, then placing the mixed fiber into the mold, applying pressure to tightly wrap the TPU around the outer layer of the fiber to form a solid protective film, and obtaining wrapped fiber;

[0025] S6: putting the wrapped fiber into a twisting machine for twisting, and gradually adding an antioxidant and a UV stabilizer during the twisting process to obtain a twisted plied yarn;

[0026] S7: The twisted plied yarn is heat treated to further consolidate the structure and eliminate internal stress to obtain the plied yarn.

[0027] As the preferred technical solution:

[0028] In the twisting process of a plied yarn as described above, in S3, the dissolved spider silk protein solution is placed in the syringe of the electrospinning machine, and the electrospinning machine is used to atomize the solution into uniform and fine droplets, and the droplets are accurately coated on each mixed fiber under the action of the electric field.

[0029] In a twisting process of a plied silk as described above, a precursor solution containing a silicon source is evenly sprayed on the fibers coated with spider silk protein, and silica aerogel is generated in situ by controlling the hydrolysis and polycondensation reactions of the precursor to fill the gaps between the fibers.

[0030] In the twisting process of the twisted yarn as described above, in S7, the twisted twisted yarn is heat treated, and the segmented heat treatment technology is used to gradually heat, keep warm and cool the twisted twisted yarn to obtain the twisted yarn.

[0031] Compared with the prior art, the present invention has the following beneficial effects:

[0032] Enhanced conductivity and flexibility: The introduction of silver nanowires significantly improves the conductivity and flexibility of the twisted yarn. This makes the twisted yarn have a wider application prospect in flexible electronic devices, such as wearable devices, smart textiles, etc., so as to achieve efficient energy and data transmission of the device while maintaining a comfortable wearing experience.

[0033] Excellent mechanical properties: The addition of bio-inspired polymers (such as spider silk protein) has made a qualitative leap in the mechanical properties of twisted silk. The high strength and toughness of spider silk protein give twisted silk better tensile strength and impact resistance, making it suitable for fields that require high-strength fiber support, such as high-performance sports equipment, protective clothing, etc.

[0034] Lightweight and thermal insulation: The integration of silica aerogel brings lightness and thermal insulation properties to the twisted yarn. This composite fiber has significant advantages in the aerospace field, which can reduce the weight of aircraft and improve their energy efficiency; at the same time, in terms of thermal insulation materials, its good thermal insulation properties help maintain a comfortable temperature environment.

[0035] Potential of multifunctional composite materials: The use of carbon fiber film TPU adds a new functional layer to the plied yarn. This material can combine the flexibility of polyurethane elastomers and the strengthening characteristics of carbon fibers, while incorporating anti-oxidation functions through modification technology. This versatility makes the plied yarn more adaptable and durable in the face of complex environments, providing more possibilities for high-end applications. BRIEF DESCRIPTION OF THE DRAWINGS

[0036] Figure 1 It is a data line chart of the embodiments and comparative examples of the present invention;

[0037] Figure 2 It is a data bar chart of the embodiments and comparative examples of the present invention. DETAILED DESCRIPTION

[0038] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the invention belongs. In the event of a conflict, the definitions in the specification shall prevail. "When mass, concentration, temperature, time, or other value or parameter is expressed as a range, a preferred range, or a range defined by a series of upper preferred values ​​and lower preferred values, this should be understood to specifically disclose all ranges formed by any pairing of any upper range limit or preferred value with any lower range limit or preferred value, regardless of whether the range is disclosed separately. For example, a range of 1-50 should be understood to include 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91 6, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50, any number, combination of numbers, or subrange, and all decimal values ​​between the above integers, for example, 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, and 1.9. With respect to subranges, "nested subranges" extending from any endpoint within the range are specifically contemplated. For example, nested subranges of the exemplary range 1-50 may include 1-10, 1-20, 1-30, and 1-40 in one direction, or 50-40, 50-30, 50-20, and 50-10 in the other direction."

[0039] The present invention is further explained below in conjunction with specific examples. The experimental methods described in the following examples are conventional methods unless otherwise specified; the reagents and materials described are all commercially available unless otherwise specified.

[0040] A twisted yarn comprises the following components in parts by weight: 25-35 parts of polyester fiber, 3-7 parts of nano silver wire, 10-20 parts of spider silk protein, 3-7 parts of silica aerogel, 15-25 parts of nylon 661, 5-15 parts of carbon fiber film TPU, 1-3 parts of antioxidant, 1-3 parts of ultraviolet stabilizer and 0.5-1.5 parts of lubricant.

[0041] Specifically, the diameter of the polyester fiber is controlled at 10-20 microns, and the crystallinity of the polyester fiber is 60%-100%; the particle size of the nano silver wire is 25-50 nanometers, and the aspect ratio is 100-450; the amino acid sequence of the spider silk protein is 80%-100% similar to the key sequence of the natural spider silk protein, and the content of the β-folded structure in the secondary structure of the spider silk protein accounts for 60%-90% of the total protein structure; the porosity of the silica aerogel is 90%-100%, and the particle size of the silica particles constituting the aerogel is 10-50 nanometers; the crystallinity of nylon 66 is 50%-80 %, the molecular weight of nylon 66 is between 20,000 and 30,000 Daltons; the diameter of the carbon fiber in the carbon fiber film TPU is between 5 and 10 microns, and the content of the carbon fiber in the film is between 30% and 70%; the antioxidant is one of tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate and dibutylhydroxytoluene, the UV stabilizer is one of 2-(2'-hydroxy-5'-methylphenyl)benzotriazole and 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, and the lubricant is one of long-chain fatty acid esters or silicone oil compounds.

[0042] The polyester fiber is chemically modified to introduce functional groups, which include hydrophilic groups or antistatic groups; the nano silver wires are linearly arranged in the plied silk, and hydrogen bonds or chemical bonds are formed between the nano silver wires and other components through surface modification, thereby enhancing interface interaction and overall stability; the molecular chains of the spider silk-like protein form a three-row parallel structure, simulating the multi-level structure of natural spider silk, and the spider silk-like protein and other polymer components form an interpenetrating network through interpenetrating network technology, thereby enhancing the composite properties of the plied silk, and the composite properties of the plied silk are set as P_c, then:

[0043] P_c=k_2\cdotD^{n_2};

[0044] Wherein, D is the density of the interpenetrating network, indicating the degree of interweaving between the spider silk protein and other polymer components; k_2 is a constant related to the material composition and processing conditions; n_2 is an index of the influence of the density of the interpenetrating network on the composite performance; during the formation of the silica aerogel, a primary pre-network and a secondary pre-network structure are constructed to optimize its pore structure and thermal insulation performance; nylon 66 is copolymerized and modified to introduce a third monomer with a toughening function.

[0045] The following is a specific embodiment, which details how to implement the various technical points in the twisted yarn:

[0046] Example

[0047] 1. Chemical modification of polyester fiber

[0048] Polyester fiber (such as PET fiber) is selected as the base material.

[0049] Functional groups such as hydrophilic groups (-OH, -COOH, etc.) or antistatic groups (-NH2, -SO3H, etc.) are introduced into polyester fibers by chemical methods. This can be achieved through chemical reactions such as transesterification, amidation or sulfonation. The modified polyester fibers have better hydrophilicity or antistatic properties to meet specific application requirements.

[0050] Data: After chemical modification, the hydrophilicity of polyester fiber increased by 30%, and the antistatic property reduced the charge accumulation rate by 50%.

[0051] 2. Arrangement and modification of silver nanowires

[0052] The silver nanowires are uniformly dispersed in a solvent to form a stable silver nanowire suspension. The silver nanowires are arranged linearly in the plied yarn through specific processing techniques (such as spraying, dipping, etc.). The silver nanowires are surface modified, such as using surfactants or polymer coatings, to enhance their compatibility with other components and to enhance interfacial interactions and overall stability by forming hydrogen bonds or chemical bonds.

[0053] Data: After surface modification, the interfacial bonding strength between nanosilver wires and other components increased by 40%, and the overall stability increased by 50%.

[0054] 3. Structure and interpenetrating network of spider silk protein

[0055] Synthesize spider silk protein and ensure that its molecular chains form three parallel rows to simulate the multi-layer structure of natural spider silk. Through interpenetrating network technology, spider silk protein and other polymer components (such as polyester fiber, nylon 66, etc.) form a tight interpenetrating network.

[0056] According to the formula P_c=k_2\cdotD^{n_2}, the composite performance Pc of the plied yarn is optimized by adjusting the density D of the interpenetrating network.

[0057] Data: k2 is set to 0.8, n2 is set to 1.2. By adjusting the D value, it is found that when D = 0.7, Pc reaches the optimal value, at which time the tensile strength of the plied yarn increases by 60% and the toughness increases by 50%.

[0058] 4. Optimization of pore structure and thermal insulation performance of silica aerogel

[0059] In the process of preparing silica aerogel, the pore structure and thermal insulation performance are optimized by constructing a primary pre-network and a secondary pre-network structure. The preparation conditions, such as pH value, temperature, concentration, etc., are adjusted to obtain the best pore structure and thermal insulation effect.

[0060] Data: The optimized silica aerogel has a 20% increase in porosity and a 30% increase in thermal insulation performance.

[0061] 5. Copolymerization modification of nylon 66

[0062] A third monomer with a toughening function, such as a compound containing a flexible chain segment, is selected and introduced into the molecular chain of nylon 66 through copolymerization to improve its toughness and impact resistance.

[0063] Data: After the introduction of the third monomer, the toughness of nylon 66 increased by 40% and the impact strength increased by 30%.

[0064] Specifically, the polyester fiber has a supramolecular self-assembly structure, forming an ordered nanoscale domain inside the fiber, thereby enhancing its mechanical properties and heat resistance, and by controlling the stereochemistry during the polymerization process, the molecular chain of the polyester fiber presents a helical conformation to improve its elasticity and resilience;

[0065] The silver nanowires are constructed with a core-shell structure, wherein the core is pure silver and the shell is a protective layer. By controlling the arrangement and connection of the silver nanowires, a multi-dimensional conductive network is formed to achieve more efficient current transmission;

[0066] The spider silk-like protein self-assembles into a nanoscale fiber array, simulating the fine structure of natural spider silk. Groups capable of forming dynamic cross-linking domains are introduced into the spider silk-like protein. These cross-linking domains can be reversibly formed and broken under stress, thereby dissipating energy and improving the impact resistance of the material.

[0067] The carbon fiber film TPU has a laminated composite structure, in which the carbon fiber layer provides strength, and the TPU layer provides flexibility and impact resistance.

[0068] The following is a specific embodiment for illustrating how to realize the above-mentioned technical features in the twisted yarn:

[0069] Example

[0070] 1. Supramolecular self-assembly structure and performance improvement of polyester fibers

[0071] Implementation method: Through precise control of stereochemistry during polymerization, the molecular chain of polyester fiber presents a helical conformation. Functional groups are introduced to promote the formation of orderly nano-scale domains inside the polyester fiber.

[0072] Data: The tensile strength of polyester fiber improved by supramolecular self-assembly structure increased by 20%. The elastic recovery rate reached 90%, which is 15% higher than that of traditional polyester fiber.

[0073] 2. Core-shell structure and multi-dimensional conductive network of silver nanowires

[0074] Implementation method: Prepare nanosilver wires with a core-shell structure, in which the core is pure silver and the shell is a stable protective layer, such as aluminum oxide or polymer. Use electric fields or chemical methods to precisely control the arrangement and connection of nanosilver wires in the strands to form a multi-dimensional conductive network.

[0075] Data: The conductivity of nano silver wires is 10% higher than that of traditional silver wires. In the multi-dimensional conductive network formed, the current transmission efficiency is increased by 25%.

[0076] 3. Nanoscale fiber arrays and dynamic cross-linking domains mimicking spider silk proteins

[0077] Implementation method: Genetically engineered spider silk proteins with self-assembly capabilities are expressed, and groups that can form dynamic cross-linking domains, such as disulfide bonds or hydrogen bonds, are introduced into the spider silk proteins.

[0078] Data: After the introduction of dynamic cross-linking domains, the impact strength of the material increased by 30%.

[0079] 4. Laminated composite structure of carbon fiber film TPU

[0080] Implementation method: Alternately stack carbon fiber layers and TPU layers to form a composite structure. Use hot pressing or bonding technology to ensure close bonding between layers.

[0081] Data: The laminated composite structure of carbon fiber film TPU is 15% higher than that of single carbon fiber. In the impact resistance test, the energy absorbed is 20% higher than that of traditional carbon fiber.

[0082] Embodiment 1

[0083] A twisted yarn comprises the following components in parts by weight: 25 parts of polyester fiber, 3 parts of nano silver wire, 10 parts of spider silk protein, 3 parts of silica aerogel, 15 parts of nylon 66, 5 parts of carbon fiber film TPU, 1 part of antioxidant (butylated hydroxytoluene), 1 part of ultraviolet stabilizer (2-(2'-hydroxy-5'-methylphenyl) benzotriazole), and 0.5 part of lubricant (long-chain fatty acid ester).

[0084] The embodiment also provides a twisting process of the plied yarn, comprising the following steps:

[0085] S1: Using the blending spinning technology, the polyester fiber and nylon 66 are mixed in a molten state and added into a twin-screw extruder. After high-temperature melting, mixing and extrusion, the temperature of the twin-screw extruder is 250°C, the screw speed is 100rpm, and then a continuous base fiber layer is formed through a spinneret. The spinneret aperture is 0.2mm and the spinneret temperature is 230°C.

[0086] S2: Using ultrasonic dispersion technology to disperse the silver nanowires, the power of the ultrasonic disperser is 500W, and the dispersion time is 30 minutes to break the agglomeration of the silver nanowires, and slowly add the dispersed silver nanowires into the base fiber layer, and add lubricant to obtain mixed fibers;

[0087] S3: The dissolved spider silk protein solution is placed in the syringe of the electrospinning machine. The voltage of the electrospinning machine is 15 kV, the flow rate of the syringe is 0.5 mL / h, and the receiving distance is 10 cm. The electrospinning machine is used to atomize the solution into uniform and fine droplets, and the droplets are precisely coated on each mixed fiber under the action of the electric field.

[0088] S4: Spraying a precursor solution containing a silicon source uniformly on the fibers coated with the spider silk protein, the concentration of the precursor solution is 0.1 mol / L, the hydrolysis temperature is 30°C, and the polycondensation reaction time is 1 hour. By controlling the hydrolysis and polycondensation reactions of the precursor, silica aerogel is generated in situ and filled in the gaps between the fibers;

[0089] S5: placing the carbon fiber film TPU in a mold of a hot press at a temperature of 180°C, heating it to above the melting point of TPU, and then placing the mixed fiber in the mold, applying pressure to tightly wrap the TPU around the outer layer of the fiber at a pressure of 5 MPa for 30 seconds to form a solid protective film to obtain wrapped fiber;

[0090] S6: putting the wrapped fiber into a twisting machine for twisting, the twisting machine speed is 500 rpm, the tension is controlled at 10 cN, and an antioxidant and a UV stabilizer are gradually added during the twisting process to obtain a twisted plied yarn;

[0091] S7: heat-treating the twisted plied yarn by adopting segmented heat treatment technology, gradually heating, keeping warm and cooling the twisted plied yarn, with an initial temperature of 100°C, a heating rate of 5°C / min, a keeping temperature of 150°C, a keeping time of 1 hour, and a cooling rate of 3°C / min to room temperature to obtain the plied yarn.

[0092] Embodiment 2

[0093] A twisted yarn comprises the following components in parts by weight: 28 parts of polyester fiber, 4 parts of nano silver wire, 12 parts of spider silk protein, 4 parts of silica aerogel, 19 parts of nylon 66, 8 parts of carbon fiber film TPU, 2 parts of antioxidant (butylated hydroxytoluene), 2 parts of ultraviolet stabilizer (2-(2'-hydroxy-5'-methylphenyl) benzotriazole), and 0.7 parts of lubricant (long-chain fatty acid ester).

[0094] The embodiment also provides a twisting process of the plied yarn, comprising the following steps:

[0095] S1: Using the blending spinning technology, the polyester fiber and nylon 66 are mixed in a molten state and added into a twin-screw extruder. After high-temperature melting, mixing and extrusion, the temperature of the twin-screw extruder is 260°C, the screw speed is 120rpm, and then a continuous base fiber layer is formed through a spinneret. The spinneret aperture is 0.3mm and the spinneret temperature is 240°C.

[0096] S2: Using ultrasonic dispersion technology to disperse the silver nanowires, the power of the ultrasonic disperser is 600W, and the dispersion time is 35 minutes, so as to break the agglomeration state of the silver nanowires, slowly add the dispersed silver nanowires into the base fiber layer, and add lubricant to obtain mixed fibers;

[0097] S3: The dissolved spider silk protein solution is placed in the syringe of the electrospinning machine. The voltage of the electrospinning machine is 18 kV, the flow rate of the syringe is 0.8 mL / h, and the receiving distance is 13 cm. The electrospinning machine is used to atomize the solution into uniform and fine droplets, and the droplets are precisely coated on each mixed fiber under the action of the electric field.

[0098] S4: Spraying a precursor solution containing a silicon source uniformly on the fibers coated with the spider silk protein, the concentration of the precursor solution is 0.2 mol / L, the hydrolysis temperature is 35°C, and the polycondensation reaction time is 2 hours. By controlling the hydrolysis and polycondensation reactions of the precursor, silica aerogel is generated in situ and filled in the gaps between the fibers;

[0099] S5: placing the carbon fiber film TPU in a mold of a hot press at a temperature of 190°C, heating it to above the melting point of TPU, and then placing the mixed fiber in the mold, applying pressure to tightly wrap the TPU around the outer layer of the fiber at a pressure of 8MPa for 50 seconds to form a solid protective film to obtain wrapped fiber;

[0100] S6: putting the wrapped fiber into a twisting machine for twisting, the twisting machine speed is 800 rpm, the tension is controlled at 15 cN, and an antioxidant and a UV stabilizer are gradually added during the twisting process to obtain a twisted plied yarn;

[0101] S7: heat-treating the twisted plied yarn by adopting segmented heat treatment technology, gradually heating, keeping warm and cooling the twisted plied yarn, with an initial temperature of 100°C, a heating rate of 5°C / min, a keeping temperature of 150°C, a keeping time of 1 hour, and a cooling rate of 3°C / min to room temperature to obtain the plied yarn.

[0102] Embodiment 3

[0103] A twisted yarn comprises the following components in parts by weight: 32 parts of polyester fiber, 5 parts of nano silver wire, 16 parts of spider silk protein, 6 parts of silica aerogel, 22 parts of nylon 66, 12 parts of carbon fiber film TPU, 2 parts of antioxidant (butylated hydroxytoluene), 2 parts of ultraviolet stabilizer (2-(2'-hydroxy-5'-methylphenyl) benzotriazole), and 1.2 parts of lubricant (long-chain fatty acid ester).

[0104] The embodiment also provides a twisting process of the plied yarn, comprising the following steps:

[0105] S1: Using the blending spinning technology, the polyester fiber and nylon 66 are mixed in a molten state and added into a twin-screw extruder. After high-temperature melting, mixing and extrusion, the temperature of the twin-screw extruder is 270°C, the screw speed is 180rpm, and then a continuous base fiber layer is formed through a spinneret. The spinneret aperture is 0.4mm and the spinneret temperature is 250°C.

[0106] S2: Using ultrasonic dispersion technology to disperse the silver nanowires, the power of the ultrasonic disperser is 800W, the dispersion time is 50 minutes, the agglomeration state of the silver nanowires is broken, and the dispersed silver nanowires are slowly added to the base fiber layer, and lubricants are added to obtain mixed fibers;

[0107] S3: The dissolved spider silk protein solution is placed in the syringe of the electrospinning machine. The voltage of the electrospinning machine is 22 kV, the flow rate of the syringe is 1.5 mL / h, and the receiving distance is 17 cm. The electrospinning machine is used to atomize the solution into uniform and fine droplets, and the droplets are precisely coated on each mixed fiber under the action of the electric field.

[0108] S4: Spraying a precursor solution containing a silicon source uniformly on the fibers coated with the spider silk protein, the concentration of the precursor solution is 0.4 mol / L, the hydrolysis temperature is 50°C, and the polycondensation reaction time is 2 hours. By controlling the hydrolysis and polycondensation reactions of the precursor, silica aerogel is generated in situ and filled in the gaps between the fibers;

[0109] S5: placing the carbon fiber film TPU in a mold of a hot press at a temperature of 210°C, heating it to above the melting point of TPU, and then placing the mixed fiber in the mold, applying pressure to tightly wrap the TPU around the outer layer of the fiber at a pressure of 12 MPa for 70 seconds to form a solid protective film to obtain wrapped fiber;

[0110] S6: putting the wrapped fiber into a twisting machine for twisting, the twisting machine speed is 1200 rpm, the tension is controlled at 20 cN, and an antioxidant and a UV stabilizer are gradually added during the twisting process to obtain a twisted plied yarn;

[0111] S7: heat-treating the twisted plied yarn by adopting segmented heat treatment technology, gradually heating, keeping warm and cooling the twisted plied yarn, with an initial temperature of 100°C, a heating rate of 5°C / min, a keeping temperature of 150°C, a keeping time of 1 hour, and a cooling rate of 3°C / min to room temperature to obtain the plied yarn.

[0112] Embodiment 4

[0113] A twisted yarn comprises the following components in parts by weight: 35 parts of polyester fiber, 7 parts of nano silver wire, 20 parts of spider silk protein, 7 parts of silica aerogel, 25 parts of nylon 66, 15 parts of carbon fiber film TPU, 3 parts of antioxidant (butylated hydroxytoluene), 3 parts of ultraviolet stabilizer (2-(2'-hydroxy-5'-methylphenyl) benzotriazole), and 1.5 parts of lubricant (long-chain fatty acid ester).

[0114] The embodiment also provides a twisting process of the plied yarn, comprising the following steps:

[0115] S1: Using the blending spinning technology, the polyester fiber and nylon 66 are mixed in a molten state and added into a twin-screw extruder. After high-temperature melting, mixing and extrusion, the temperature of the twin-screw extruder is 280°C, the screw speed is 200rpm, and then a continuous base fiber layer is formed through a spinneret. The spinneret aperture is 0.5mm and the spinneret temperature is 260°C.

[0116] S2: Using ultrasonic dispersion technology to disperse the silver nanowires, the power of the ultrasonic disperser is 1000W, the dispersion time is 60 minutes, the agglomeration state of the silver nanowires is broken, and the dispersed silver nanowires are slowly added to the base fiber layer, and lubricants are added to obtain mixed fibers;

[0117] S3: The dissolved spider silk protein solution is placed in the syringe of the electrospinning machine. The voltage of the electrospinning machine is 25 kV, the flow rate of the syringe is 2 mL / h, and the receiving distance is 20 cm. The electrospinning machine is used to atomize the solution into uniform and fine droplets, and the droplets are precisely coated on each mixed fiber under the action of the electric field.

[0118] S4: Spraying a precursor solution containing a silicon source uniformly on the fibers coated with the spider silk protein, the concentration of the precursor solution is 0.5 mol / L, the hydrolysis temperature is 60°C, and the polycondensation reaction time is 3 hours. By controlling the hydrolysis and polycondensation reactions of the precursor, silica aerogel is generated in situ and filled in the gaps between the fibers;

[0119] S5: placing the carbon fiber film TPU in a mold of a hot press at a temperature of 220°C, heating it to above the melting point of TPU, and then placing the mixed fiber in the mold, applying pressure to tightly wrap the TPU around the outer layer of the fiber at a pressure of 15 MPa for 90 seconds to form a solid protective film to obtain wrapped fiber;

[0120] S6: putting the wrapped fiber into a twisting machine for twisting, the twisting machine speed is 1500 rpm, the tension is controlled at 30 cN, and an antioxidant and a UV stabilizer are gradually added during the twisting process to obtain a twisted plied yarn;

[0121] S7: heat-treating the twisted plied yarn by adopting segmented heat treatment technology, gradually heating, keeping warm and cooling the twisted plied yarn, with an initial temperature of 100°C, a heating rate of 5°C / min, a keeping temperature of 150°C, a keeping time of 1 hour, and a cooling rate of 3°C / min to room temperature to obtain the plied yarn.

[0122] Comparative Example 1

[0123] A twisted yarn and twisting process thereof are basically the same as those of the fourth embodiment, except that the addition of nano silver wire is omitted during the preparation of the twisted yarn.

[0124] Comparative Example 2

[0125] A twisted yarn and twisting process thereof are basically the same as those of the fourth embodiment, except that the addition of spider silk-like protein is omitted during the preparation of the twisted yarn.

[0126] Comparative Example 3

[0127] A twisted yarn and a twisting process thereof are basically the same as those of the fourth embodiment, except that the addition of silica aerogel is omitted during the preparation of the twisted yarn.

[0128] Comparative Example 4

[0129] A plied yarn and a twisting process thereof are basically the same as those of the fourth embodiment, except that: in the preparation process of the plied yarn, the wrapping step of the carbon fiber film TPU is omitted.

[0130] The twisted yarns prepared in the above-mentioned Examples 1 to 4 and Comparative Examples 1 to 4 were tested:

[0131] Tensile strength and elongation: GB / T 14337-2008 "Test method for tensile properties of chemical staple fibers"

[0132] Testing method: Use a tensile testing machine to perform tensile tests on fiber samples and record the strength and elongation at break.

[0133] Abrasion resistance: GB / T 11047-2008 "Test method for color fastness to abrasion of textiles"

[0134] Testing method: Use a friction tester to simulate the friction of the fiber in actual use and evaluate its color fastness.

[0135] Color fastness to washing: GB / T 3921-2008 "Textiles - Tests for color fastness - Color fastness to washing with soap"

[0136] Test method: Simulate the color change of fibers during washing to evaluate their color fastness to washing.

[0137] Chemical composition analysis: According to the specific composition of the fiber, the standards involved include GB / T2910-2009 "Quantitative Chemical Analysis of Textiles".

[0138] Testing method: Analyze the composition of the fiber by chemical methods to ensure compliance with relevant standards.

[0139] The results are shown in Table 1:

[0140] Table 1

[0141]

[0142]

[0143] From the above Table 1, it can be seen that as the weight fractions of each component from Example 1 to Example 4 increase, and the corresponding processing conditions are adjusted, the tensile strength of the plied yarn gradually increases. Example 4 shows the highest tensile strength, reaching 380MPa, and the elongation also gradually increases with the progress of the examples. The elongation of Example 4 reaches 45%, indicating that the plied yarn can maintain good deformation ability when stretched and is not easy to break. The color fastness to friction is an indicator to measure the color retention ability of the material during the friction process. It can be seen from the data that the color fastness to friction of all embodiments is maintained at a high level of 4-5, which shows that the color stability of the plied yarn is very good and is not easy to fade even under friction conditions. The color fastness to washing of Example 1 is 4-5, while Examples 2 to 4 all reach the highest standard of 5. This shows that with the optimization of components and processing technology, the color fastness to washing of the plied yarn has also been significantly improved. In summary, the plied yarns of Examples 1 to 4 show obvious excellent performance in various performance indicators.

[0144] Reference Figure 1-2 In the comparison between Example 4 and Comparative Example 1, after omitting the nano silver wire in Comparative Example 1, the tensile strength and elongation of the plied yarn decreased slightly, while the addition of the nano silver wire significantly increased the tensile strength and elongation of the plied yarn. This is because the nano silver wire enhanced the internal structure of the fiber and improved its mechanical properties. At the same time, the nano silver wire also helps to improve the color fastness to washing, which is achieved by improving the properties of the fiber surface.

[0145] In the comparison between Example 4 and Comparative Example 2, after the spider silk protein was omitted in Comparative Example 2, the tensile strength and elongation of the plied silk decreased significantly, indicating that the spider silk protein is essential for improving the strength and toughness of the fiber. The addition of spider silk protein has a significant improvement effect on the tensile strength, elongation and color fastness (including friction resistance and washing resistance) of the plied silk. This is because the spider silk protein has excellent mechanical properties and good film-forming properties, which can effectively enhance the structure of the fiber and protect it from damage from the external environment.

[0146] Comparison between Example 4 and Comparative Example 3 shows that after omitting silica aerogel in Comparative Example 3, the tensile strength and elongation of the plied silk slightly decreased, but not as significantly as when the mimetic spider silk protein was omitted. The introduction of silica aerogel also had a positive effect on the tensile strength, elongation and color fastness of the plied silk. This is attributed to the filling of the gaps between the fibers by silica aerogel, which enhances the overall structural stability of the fiber and improves its ability to resist external friction and washing.

[0147] After omitting the carbon fiber film TPU in comparative example 4, the tensile strength and elongation of the plied yarn decreased significantly, indicating that the carbon fiber film TPU plays an important role in enhancing the overall strength of the fiber. At the same time, the significant reduction in color fastness to friction and color fastness to washing also reflects the importance of the carbon fiber film TPU in protecting the fiber from external wear and washing. The wrapping of the carbon fiber film TPU has a particularly significant improvement in the performance of the plied yarn, especially in tensile strength, elongation and color fastness. This is because the carbon fiber film TPU, as a strong protective layer, greatly enhances the mechanical properties and durability of the fiber.

[0148] The present invention achieves a combination of multiple excellent properties through carefully designed components and advanced twisting technology. The main components of the twisted silk include polyester fiber, nano silver wire, spider silk protein, silica aerogel, nylon 66, carbon fiber film TPU, and additives such as antioxidants, ultraviolet stabilizers and lubricants. These components are mixed in a specific proportion and prepared through a series of process steps (such as co-spinning, ultrasonic dispersion, electrospinning, hot pressing and segmented heat treatment).

[0149] By introducing spider silk protein and silver nanowires, the tensile strength and toughness of the plied silk were significantly improved. The high strength and toughness of spider silk protein and the reinforcing effect of silver nanowires jointly improved the overall mechanical properties of the fiber.

[0150] The wrapping of carbon fiber film TPU further enhances the strength and durability of the fiber, enabling it to withstand higher tensile force and impact force.

[0151] The addition of nano silver wires gives the twisted silk good conductivity, making it suitable for use in areas such as flexible electronic devices.

[0152] At the same time, the combination of nano silver wire and the flexibility of polyester fiber enables the twisted yarn to maintain high strength while also having good flexibility, making it easy to process and apply.

[0153] The addition of silica aerogel gives the twisted yarn an extremely low density and good thermal insulation performance, making it suitable for aerospace, thermal insulation materials and other fields.

[0154] This lightweight insulation helps reduce product weight, improves energy efficiency, and increases product comfort.

[0155] The addition of antioxidants and UV stabilizers effectively extends the service life of the twisted yarn and improves its weather resistance and stability.

[0156] These additives resist damage from oxidation and UV rays, keeping the fiber's performance stable over the long term.

[0157] As a bioinspired polymer, spider silk protein has good biocompatibility and is suitable for use in the medical and biotechnology fields.

[0158] The materials and processes used in the entire preparation process also tend to be environmentally friendly and sustainable, meeting the requirements of modern industry for green production.

[0159] Due to the excellent performance of twisted yarn in mechanical properties, conductivity, thermal insulation, durability and biocompatibility, it has broad application prospects in many fields such as textile, aerospace, military, and medical.

[0160] The above description is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A twisted yarn, characterized in that: The invention comprises the following components in parts by weight: 25-35 parts of polyester fiber, 3-7 parts of nano silver wire, 10-20 parts of spider silk protein, 3-7 parts of silica aerogel, 15-25 parts of nylon 661, 5-15 parts of carbon fiber film TPU, 1-3 parts of antioxidant, 1-3 parts of ultraviolet stabilizer and 0.5-1.5 parts of lubricant.

2. A twisted yarn according to claim 1, characterized in that: The invention comprises the following components in parts by weight: 28 parts of polyester fiber, 4 parts of nano silver wire, 13 parts of spider silk protein, 4 parts of silica aerogel, 18 parts of nylon 66, 7 parts of carbon fiber film TPU, 2 parts of antioxidant, 2 parts of ultraviolet stabilizer and 0.9 parts of lubricant.

3. A twisted yarn according to claim 1, characterized in that: The diameter of the polyester fiber is controlled to be 10-20 microns, and the crystallinity of the polyester fiber is 60%-100%; The particle size of the nano silver wire is 25-50 nanometers, and the aspect ratio is 100-450; The amino acid sequence of the spider silk-mimicking protein has a similarity of 80% to 100% with the key sequence of the natural spider silk protein, and the content of the β-folded structure in the secondary structure of the spider silk-mimicking protein accounts for 60% to 90% of the total protein structure; The porosity of the silica aerogel is 90%-100%, and the particle size of the silica particles constituting the aerogel is 10-50 nanometers; The crystallinity of the nylon 66 is 50%-80%, and the molecular weight of the nylon 66 is 20,000-30,000 Daltons; The diameter of the carbon fiber in the carbon fiber film TPU is 5-10 microns, and the content of the carbon fiber in the film is 30%-70%; The antioxidant is one of tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate] pentaerythritol ester and dibutylhydroxytoluene, the ultraviolet stabilizer is one of 2-(2'-hydroxy-5'-methylphenyl)benzotriazole and 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole, and the lubricant is one of long-chain fatty acid esters or silicone oil compounds.

4. A twisted yarn according to claim 1, characterized in that: The polyester fiber is chemically modified to introduce functional groups, wherein the functional groups include hydrophilic groups or antistatic groups; The nano silver wires are arranged linearly in the plied yarn, and hydrogen bonds or chemical bonds are formed between the nano silver wires and other components through surface modification, thereby enhancing interface interaction and overall stability; The molecular chains of the spider silk-like protein form a structure of three rows parallel to each other, simulating the multi-layer structure of natural spider silk. Through the interpenetrating network technology, the spider silk-like protein and other polymer components form an interpenetrating network to enhance the composite properties of the stranded silk. The composite properties of the stranded silk are set as P_c, then: P_c=k_2\cdotD^{n_2}; Where D is the density of the interpenetrating network, which indicates the degree of interweaving between the spider silk protein and other polymer components; k_2 is a constant related to the material composition and processing conditions; n_2 is the index of the influence of the interpenetrating network density on the composite performance; During the formation of the silica aerogel, a primary pre-network and a secondary pre-network structure are constructed to optimize its pore structure and thermal insulation performance; Nylon 66 is copolymerized and modified by introducing a third monomer with toughening function.

5. The twisted yarn according to claim 1, characterized in that: The polyester fiber has a supramolecular self-assembly structure, forming an ordered nano-scale domain inside the fiber, thereby enhancing its mechanical properties and heat resistance, and by controlling the stereochemistry during the polymerization process, the molecular chain of the polyester fiber presents a helical conformation, thereby improving its elasticity and resilience; The silver nanowires are constructed with a core-shell structure, wherein the core is pure silver and the shell is a protective layer. By controlling the arrangement and connection of the silver nanowires, a multi-dimensional conductive network is formed to achieve more efficient current transmission. The spider silk-like protein self-assembles into a nanoscale fiber array, simulating the fine structure of natural spider silk. Groups capable of forming dynamic cross-linking domains are introduced into the spider silk-like protein. These cross-linking domains can be reversibly formed and broken under stress, thereby dissipating energy and improving the impact resistance of the material. The carbon fiber film TPU has a laminated composite structure, in which the carbon fiber layer provides strength, and the TPU layer provides flexibility and impact resistance.

6. A twisting process for a plied yarn according to any one of claims 1 to 5, characterized in that: The following steps are involved: S1: Using the co-spinning technology, polyester fiber and nylon 66 are mixed in a molten state and added into a twin-screw extruder. After high-temperature melting, mixing, and extrusion, a continuous base fiber layer is formed through a spinneret. S2: Using ultrasonic dispersion technology to disperse the silver nanowires, breaking the agglomeration of the silver nanowires, slowly adding the dispersed silver nanowires into the base fiber layer, and adding lubricants to obtain mixed fibers; S3: evenly coating the dissolved spider silk protein solution on the mixed fiber, and using a coating device to ensure that each fiber is evenly coated; S4: Add silica aerogel to the fibers coated with spider silk protein, and use the porous structure of aerogel to enhance the thermal insulation performance of the twisted silk; S5: placing the carbon fiber film TPU in a mold of a hot press, heating it to above the melting point of TPU, then placing the mixed fiber into the mold, applying pressure to tightly wrap the TPU around the outer layer of the fiber to form a solid protective film, and obtaining wrapped fiber; S6: putting the wrapped fiber into a twisting machine for twisting, and gradually adding an antioxidant and a UV stabilizer during the twisting process to obtain a twisted plied yarn; S7: The twisted plied yarn is heat treated to further consolidate the structure and eliminate internal stress to obtain the plied yarn.

7. A twisting process for a plied yarn according to claim 6, characterized in that: In S3, the dissolved spider silk protein solution is placed in a syringe of an electrospinning machine, and the electrospinning machine is used to atomize the solution into uniform and fine droplets, which are then precisely coated on each mixed fiber under the action of an electric field.

8. A twisting process for a plied yarn according to claim 6, characterized in that: In the above S4, a precursor solution containing a silicon source is uniformly sprayed on the fibers coated with the spider silk protein, and the hydrolysis and polycondensation reactions of the precursor are controlled to generate silica aerogel in situ and fill the gaps between the fibers.

9. A twisting process for a plied yarn according to claim 6, characterized in that: In S7, the twisted plied yarn is heat treated by gradually heating, keeping warm and cooling the twisted plied yarn using a segmented heat treatment technology to obtain the plied yarn.

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