Anti-radiation degradable environment-friendly clothing material and manufacturing process thereof

Abstract

The invention discloses an anti-radiation degradable environment-friendly clothing material and a manufacturing process thereof. According to the invention, a multi-level electromagnetic shielding system in the material efficiently blocks various electromagnetic wave radiation, and meanwhile, the bionic groove structure greatly reduces radiation residue and liquid adhesion, so that the dual effects of fouling prevention and adsorption resistance are realized. The nano-scale interpenetrating network endows the fabric with excellent air permeability and maintains the characteristic of high strength, the added bioactive components endow the material with long-acting antibacterial ability, and wear health and safety are guaranteed from the source. Bio-based raw materials and a cleaning process are adopted in the whole process, emission of toxic chemical substances is avoided, and after being discarded, the material can be quickly and naturally decomposed without generating micro-plastic pollution. According to the energy-saving manufacturing technology, production energy consumption is greatly reduced, efficient resource circulation is achieved through the waste regeneration technology, an ecological closed loop from production to use to recovery is formed, and deep integration of environment friendliness and sustainable development is truly achieved.

Description

Technical Field

[0001] The present invention belongs to the technical field of clothing materials, and specifically relates to a radiation-proof and degradable environmentally friendly clothing material and its manufacturing process. Background Art

[0002] Degradable environmentally friendly clothing materials are a type of clothing fabric made from bio-based materials or degradable synthetic materials, aiming to reduce environmental pollution and resource consumption. These materials can decompose into water, carbon dioxide, and other harmless substances through the action of microorganisms under natural conditions, without causing long-term pollution to soil and water sources. Common degradable environmentally friendly clothing materials include regenerated cellulose fibers, polylactic acid fibers, etc. They have good air permeability, moisture absorption, and comfort, while reducing the clothing industry's dependence on fossil energy and promoting sustainable development. Using degradable environmentally friendly clothing materials helps protect the ecological environment and is an important development direction for the future clothing industry.

[0003] Existing radiation-proof materials mostly rely on metal components or chemical coatings, having problems such as high weight, poor air permeability, easy oxidation and failure, and limited service life due to lack of self-repair ability, and antibacterial treatment often relies on heavy metals, leading to environmental risks. Summary of the Invention

[0004] The purpose of the present invention is to provide a radiation-proof and degradable environmentally friendly clothing material and its manufacturing process to solve the above-mentioned problems.

[0005] The technical solution adopted by the present invention is as follows: A radiation-proof and degradable environmentally friendly clothing material, the radiation-proof and degradable environmentally friendly clothing material includes:

[0006] 40 parts of sodium alginate / polylactic acid composite nanofibers, 25 parts of polypyrrole conductive nanofibers, 15 parts of chitin nanocrystals, 10 parts of bismuth tungstate nanosheets, 8 parts of silver nanowire / graphene composite, 12 parts of zein modified coating agent, 7 parts of sharkskin-like microgroove structure layer, 5 parts of bioactive carbon nanospheres, 3 parts of natural tannic acid crosslinking agent, 6 parts of silk fibroin self-repairing emulsion;

[0007] Among them, the bismuth tungstate nanosheets are synthesized by a hydrothermal method and have a lamellar structure with exposed crystal planes; the sharkskin-like microgroove structure layer is prepared by 3D printing photocuring technology, and the groove depth is 50 - 80 μm; the bioactive carbon nanospheres are prepared from waste coconut shells by microbial activation method, and the specific surface area ≥ 2000m 2 / g.

[0008] In a preferred embodiment, the manufacturing process includes:

[0009] S1: Adopt the meltblown - electrospinning composite process to form a three - dimensional interpenetrating network structure of sodium alginate / polylactic acid composite nanofibers and polypyrrole conductive fibers in an alternating electric field, controlling the melt temperature at 185 °C and the electric field strength at 25 kV / cm;

[0010] S2: Deposit a bismuth tungstate / graphene composite film on the substrate surface through magnetron sputtering technology, with a target power of 300 W and an argon pressure of 0.8 Pa, to form a gradient shielding layer with a thickness of 200 nm;

[0011] S3: Use microfluidic chip technology to prepare a chitin nanocrystal suspension and conduct in - situ self - assembly with a zein modifier in an alkaline environment with pH = 9 to form a nanoscale core - shell structure;

[0012] S4: Utilize bio - enzyme etching technology to construct bionic micro - grooves on the material surface, using immobilized papain to treat at 45 °C for 2 hours to form a directional fluid channel;

[0013] S5: Adopt the supercritical CO2 fluid penetration process to load bio - activated carbon nanospheres, with an operating pressure of 15 MPa and a temperature of 40 °C, to achieve nanoscale pore filling;

[0014] S6: Activate natural tannic acid through microwave - assisted cross - linking technology, irradiate at a frequency of 2.45 GHz for 90 seconds to initiate an intermolecular condensation reaction to form a three - dimensional cross - linked network;

[0015] S7: Apply screen - printing technology to position - deposit a silk fibroin self - healing emulsion, with a patterning accuracy of 50 μm, and form an intelligent responsive repair layer through humidity gradient treatment;

[0016] S8: Adopt low - temperature plasma grafting modification, treat in a helium / oxygen mixed atmosphere for 10 minutes, and reduce the surface energy to below 20 mN / m;

[0017] S9: Through bio - enzymatic degradation pretreatment, use a lipase / protease composite preparation to treat at 50 °C for 30 minutes to activate the biodegradation active sites of the material.

[0018] In a preferred embodiment, in step S1, a dual spinneret composite spinning system is used. The melt blown spinneret on the left sprays the sodium alginate / polylactic acid composite at an extrusion rate of 0.15 g / min at a melting temperature of 185 ± 2 °C. The electrospinning device on the right uses an 18G stainless steel needle to electrospin a DMAC solution containing 3 wt% polypyrrole at a feeding rate of 1.2 mL / h under an alternating electric field of 25 kV / cm. The receiving device uses a copper mesh roller rotating at 1200 rpm. The melt blown fibers and the electrospun fibers converge at a distance of 20 cm from the spinneret to form a three-dimensional network with a fiber diameter gradient distribution ranging from 200 nm to 5 μm. The ambient temperature and humidity are controlled at 25 ± 1 °C and 45 ± 5% RH, and continuous spinning is maintained for 2.5 hours to obtain a 0.3 mm thick substrate.

[0019] In a preferred embodiment, in step S2, a dual target magnetron sputtering device is used. The bismuth tungstate target and the graphene target are placed opposite each other at an angle of 45°. The vacuum degree of the sputtering chamber is maintained at 1 × 10^-3 Pa, and argon is introduced to make the working pressure stable at 0.8 Pa. The bismuth tungstate target is applied with a radio frequency power of 300 W, and the graphene target is applied with a direct current power of 150 W. The substrate stage rotates at a constant speed of 5 rpm. The deposition process is divided into three stages: in the initial 10 minutes, pure bismuth tungstate is deposited to form a 20 nm bottom layer; in the middle 15 minutes, the two targets are co-sputtered to form an 80 nm transition layer; and in the last 20 minutes, pure graphene is deposited to complete a 100 nm surface layer. The substrate temperature is maintained at 80 ± 2 °C throughout the process, and the deposition rate is controlled at 6.5 nm / min.

[0020] In a preferred embodiment, in step S3, a quartz glass microfluidic chip is used. The width of the main channel is 200 μm. An acetic acid solution (pH = 3) containing 5 wt% chitin nanocrystals and a Tris-HCl buffer solution (pH = 9) containing 8 wt% zein are respectively pumped into the two branches, and the flow rates are set at 15 μL / min and 30 μL / min respectively. The two-phase fluid generates vortex shear in the serpentine mixing channel, triggering an interfacial self-assembly reaction. The collection device maintains a constant temperature of 50 °C. The product is centrifuged at 12000 rpm for 10 minutes to obtain core-shell particles with a diameter of 80 - 120 nm and a shell thickness of about 15 nm.

[0021] In a preferred embodiment, in step S4, the immobilized papain (activity unit 200 U / g) is dispersed in a phosphate buffer solution with a pH of 6.8 to prepare a 3 wt% enzyme solution. The substrate is impregnated in the enzyme solution at 45 ± 0.5 °C for 120 minutes, and at the same time, an axial magnetic field of 0.6 T is applied to guide the direction of enzymatic hydrolysis. After the treated material is rinsed with deionized water, atomic force microscopy detection shows that a parallel groove array with a depth of 65 ± 8 μm and a spacing of 150 ± 20 μm is formed, and the surface roughness Ra value of the groove reaches 2.3 μm.

[0022] In a preferred embodiment, in step S5, a 5L supercritical reactor is used. Bioactive carbon nanospheres are pre-dispersed in ethanol to form a 2mg / mL suspension. At a pressure of 15MPa and a temperature of 40°C, supercritical CO2 is introduced at a flow rate of 12L / min for 60 minutes. After the permeation is completed, the pressure is slowly released at a rate of 0.5MPa / min, and the loading amount of the nanospheres in the pores reaches 23±2wt%. SEM observation shows that the pore filling rate of 50-200nm reaches 91%, and the macroporous structure remains intact.

[0023] In a preferred embodiment, in step S6, an ethanol solution containing 5wt% natural tannic acid is evenly coated on the material surface and placed in a 2450MHz microwave reactor. The set output power is 800W, the irradiation time is 90 seconds, and the peak temperature in the cavity is controlled below 75°C. A three-dimensional network layer with a thickness of about 500nm is formed on the surface of the cross-linked material. FTIR detection shows that the intensity of the characteristic phenolic hydroxyl peak decreases by 38%, and the cross-linking density increases to 3.2×10^20 bonds / cm 3 。

[0024] In a preferred embodiment, in step S7, a 300-mesh stainless steel wire mesh is used, and the screen pattern is made by ultraviolet lithography technology with a minimum line width of 50μm. The viscosity of the silk fibroin emulsion is adjusted to 3500±200mPa·s, the blade pressure is set at 0.25MPa, and printing is carried out at a speed of 10mm / s. The printed material is treated in a stepped humidity increase environment of 30%→60% for 4 hours, and the content of the β-sheet structure in the emulsion increases from 12% to 47%, forming an 8±1μm thick intelligent response layer.

[0025] In a preferred embodiment, in step S8, a mixed gas with a volume ratio of helium to oxygen of 4:1 is introduced into the radio frequency plasma equipment, and the working pressure is maintained at 40Pa. A 13.56MHz radio frequency power supply is applied, and the power density is set at 1.5W / cm 2 ,and the treatment time is strictly controlled at 600 seconds. The oxygen element content on the surface of the treated material increases from 8.3% to 22.1%. The water contact angle test shows that the water contact angle reaches 152°, and the rolling angle is less than 5°.

[0026] In step S9, a composite enzyme solution containing lipase (5000U / g) and protease (3000U / g) is prepared, and the mass ratio of the enzyme to the material is 1:20. It is treated in a 50°C circulating water bath for 30 minutes, and the pH value of the treatment solution is automatically stabilized at 7.8±0.2. The buried experiment of the activated material in the simulated soil environment shows that visible degradation signs start to appear on the 14th day, the weight loss rate reaches 67% in 90 days, and the molecular weight distribution broadens from the initial PDI of 1.8 to 3.2.

[0027] In summary, due to the adoption of the above technical solutions, the beneficial effects of the present invention are as follows:

[0028] 1. In the present invention, through innovative material compounding and structural design, the wearing protection performance and comfort are significantly improved. The multi-level electromagnetic shielding system inside the material effectively blocks various electromagnetic wave radiations. At the same time, the bionic groove structure greatly reduces radiation residues and liquid adhesion, achieving the dual effects of anti-fouling and anti-adsorption. The nano-scale interpenetrating network endows the fabric with excellent breathability while maintaining high strength characteristics. The intelligent self-healing function can automatically repair minor damages and extend the service life of the product. The addition of bioactive ingredients enables the material to have long-term antibacterial ability, ensuring the health and safety of wearing from the source.

[0029] 2. In the present invention, bio-based raw materials and clean processes are adopted throughout the process, avoiding the emission of toxic chemicals. After being discarded, it can be quickly decomposed naturally without generating microplastic pollution. The energy-saving manufacturing technology greatly reduces production energy consumption, and the waste recycling technology realizes efficient resource recycling. The degradation products of the material can nourish the soil, forming an ecological closed loop from production, use to recycling, truly achieving the deep integration of environmental friendliness and sustainable development. BRIEF DESCRIPTION OF THE DRAWINGS

[0030] Figure 1 It is a schematic diagram of the process principle of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0031] In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below with reference to the drawings and embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0032] Refer to Figure 1 ,

[0033] A radiation-proof and degradable environmentally friendly clothing material and its manufacturing process. The radiation-proof and degradable environmentally friendly clothing material includes:

[0034] 40 parts of sodium alginate / polylactic acid composite nanofibers, 25 parts of polypyrrole conductive nanofibers, 15 parts of chitin nanocrystals, 10 parts of bismuth tungstate nanosheets, 8 parts of silver nanowire / graphene composite, 12 parts of zein modified coating agent, 7 parts of sharkskin-like microgroove structure layer, 5 parts of bioactive carbon nanospheres, 3 parts of natural tannic acid crosslinking agent, 6 parts of silk fibroin self-healing emulsion;

[0035] Among them, the bismuth tungstate nanosheets are synthesized by a hydrothermal method and have a lamellar structure with the {001} crystal plane exposed; the sharkskin-like microgroove structure layer is prepared by a 3D printing photocuring technology, and the groove depth is 50-80 μm; the bioactive carbon nanospheres are prepared from waste coconut shells by a microbial activation method, and the specific surface area ≥ 2000 m 2 / g.

[0036] The manufacturing process includes:

[0037] S1: Adopt the meltblown - electrospinning composite process to form a three - dimensional interpenetrating network structure of sodium alginate / polylactic acid composite nanofibers and polypyrrole conductive fibers in an alternating electric field, controlling the melt temperature at 185°C and the electric field strength at 25 kV / cm;

[0038] S2: Deposit a bismuth tungstate / graphene composite film on the surface of the substrate through magnetron sputtering technology, with a target power of 300 W, an argon pressure of 0.8 Pa, to form a gradient shielding layer with a thickness of 200 nm;

[0039] S3: Use microfluidic chip technology to prepare a chitin nanocrystal suspension, and conduct in - situ self - assembly with a zein modifier in an alkaline environment with pH = 9 to form a nanoscale core - shell structure;

[0040] S4: Utilize bio - enzyme etching technology to construct bionic micro - grooves on the material surface, and use immobilized papain to treat at 45°C for 2 hours to form a directional fluid channel;

[0041] S5: Adopt the supercritical CO2 fluid penetration process to load bio - activated carbon nanospheres, with an operating pressure of 15 MPa and a temperature of 40°C to achieve nanoscale pore filling;

[0042] S6: Activate natural tannic acid through microwave - assisted cross - linking technology, irradiate at a frequency of 2.45 GHz for 90 seconds to initiate an intermolecular condensation reaction to form a three - dimensional cross - linked network;

[0043] S7: Apply screen - printing technology to position - deposit a silk fibroin self - repairing emulsion, with a patterning accuracy of 50 μm, and form an intelligent responsive repair layer through humidity gradient treatment;

[0044] S8: Adopt low - temperature plasma grafting modification, treat in a helium / oxygen mixed atmosphere for 10 minutes, and reduce the surface energy to below 20 mN / m;

[0045] S9: Through bio - enzymatic degradation pretreatment, use a lipase / protease composite preparation to treat at 50°C for 30 minutes to activate the biodegradation active sites of the material.

[0046] In step S1, a dual spinneret composite spinning system is adopted. The melt blown spinneret on the left extrudes the sodium alginate / polylactic acid composite at a melt temperature of 185 ± 2 °C with an extrusion rate of 0.15 g / min. The electrospinning device on the right uses an 18G stainless steel needle to electrospin a DMAC solution containing 3 wt% polypyrrole at a feeding rate of 1.2 mL / h under the action of an alternating electric field of 25 kV / cm. The receiving device uses a copper mesh roller with a rotation speed of 1200 rpm. The melt blown fibers and the electrospun fibers converge at a distance of 20 cm from the spinneret to form a three-dimensional network with a fiber diameter gradient distribution ranging from 200 nm to 5 μm. The ambient temperature and humidity are controlled at 25 ± 1 °C and 45 ± 5% RH, and continuous spinning is maintained for 2.5 hours to obtain a 0.3 mm thick substrate.

[0047] In step S2, a dual-target magnetron sputtering device is used. The bismuth tungstate target and the graphene target are placed opposite each other at an angle of 45°. The vacuum degree of the sputtering chamber is maintained at 1 × 10^-3 Pa, and argon is introduced to make the working pressure stable at 0.8 Pa. A radio frequency power of 300 W is applied to the bismuth tungstate target, and a DC power of 150 W is applied to the graphene target. The substrate stage rotates at a constant speed of 5 rpm. The deposition process is divided into three stages: in the initial 10 minutes, pure bismuth tungstate is deposited to form a 20 nm bottom layer; in the middle 15 minutes, the two targets are co-sputtered to form an 80 nm transition layer; in the last 20 minutes, pure graphene is deposited to complete a 100 nm surface layer. The substrate temperature is maintained at 80 ± 2 °C throughout the process, and the deposition rate is controlled at 6.5 nm / min.

[0048] In step S3, a quartz glass microfluidic chip is adopted. The width of the main channel is 200 μm. An acetic acid solution (pH = 3) containing 5 wt% chitin nanocrystals and a Tris-HCl buffer solution (pH = 9) containing 8 wt% zein are respectively pumped into the two branches, and the flow rates are set at 15 μL / min and 30 μL / min respectively. The two-phase fluids generate vortex shear in the serpentine mixing channel, triggering an interfacial self-assembly reaction. The collection device maintains a constant temperature of 50 °C. The product is centrifuged at 12000 rpm for 10 minutes to obtain core-shell particles with a diameter of 80 - 120 nm and a shell thickness of about 15 nm.

[0049] In step S4, the immobilized papain (activity unit 200 U / g) is dispersed in a phosphate buffer solution with a pH of 6.8 to prepare a 3 wt% enzyme solution. The substrate is impregnated in the enzyme solution at 45 ± 0.5 °C for 120 minutes, and at the same time, an axial magnetic field of 0.6 T is applied to guide the direction of enzymatic hydrolysis. After the treated material is rinsed with deionized water, atomic force microscope detection shows that a parallel groove array with a depth of 65 ± 8 μm and a spacing of 150 ± 20 μm is formed, and the surface roughness Ra value of the groove reaches 2.3 μm.

[0050] In step S5, a supercritical reactor with a volume of 5 L was used. Bioactive carbon nanospheres were pre-dispersed in ethanol to form a 2 mg / mL suspension. Under the conditions of a pressure of 15 MPa and a temperature of 40 °C, supercritical CO2 was introduced at a flow rate of 12 L / min for 60 minutes. After the penetration, the pressure was slowly released at a rate of 0.5 MPa / min, and the loading amount of the nanospheres in the pores reached 23 ± 2 wt%. SEM observation showed that the pore filling rate of 50 - 200 nm reached 91%, and the macroporous structure remained intact.

[0051] In step S6, an ethanol solution containing 5 wt% natural tannic acid was evenly coated on the material surface and placed in a 2450 MHz microwave reactor. The output power was set at 800 W, the irradiation time was 90 seconds, and the peak temperature in the cavity was controlled below 75 °C. A three-dimensional network layer with a thickness of about 500 nm was formed on the surface of the cross-linked material. FTIR detection showed that the intensity of the characteristic phenolic hydroxyl peak decreased by 38%, and the cross-linking density increased to 3.2×10^20 bonds / cm 3 。

[0052] In step S7, a 300-mesh stainless steel wire mesh was used, and the screen pattern was made by ultraviolet lithography technology with a minimum line width of 50 μm. The viscosity of the silk fibroin emulsion was adjusted to 3500 ± 200 mPa·s, the doctor blade pressure was set at 0.25 MPa, and printing was carried out at a speed of 10 mm / s. The printed material was treated in a stepwise humidification environment of 30% → 60% for 4 hours, and the content of β-sheet structure in the emulsion increased from 12% to 47%, forming an 8 ± 1 μm thick intelligent response layer.

[0053] In step S8, a mixed gas with a volume ratio of helium to oxygen of 4:1 was introduced into the radio frequency plasma equipment, and the working pressure was maintained at 40 Pa. A 13.56 MHz radio frequency power supply was applied, and the power density was set at 1.5 W / cm 2 , and the treatment time was strictly controlled at 600 seconds. The oxygen element content on the surface of the treated material increased from 8.3% to 22.1%. Contact angle measurement showed that the water contact angle reached 152°, and the rolling angle was less than 5°.

[0054] In step S9, a composite enzyme solution containing lipase (5000 U / g) and protease (3000 U / g) was prepared, and the mass ratio of the enzyme to the material was 1:20. It was treated in a 50 °C circulating water bath for 30 minutes, and the pH value of the treatment solution was automatically stabilized at 7.8 ± 0.2. The buried experiment of the activated material in the simulated soil environment showed that visible degradation signs began to appear on the 14th day, the weight loss rate reached 67% after 90 days, and the molecular weight distribution broadened from the initial PDI of 1.8 to 3.2.

[0055] As can be seen from the above: In the present invention, through innovative material compounding and structural design, the wearing protection performance and comfort are significantly improved. The multi-level electromagnetic shielding system inside the material effectively blocks various electromagnetic wave radiations. At the same time, the bionic groove structure greatly reduces radiation residues and liquid adhesion, achieving the dual effects of anti-fouling and anti-adsorption. The nano-level interpenetrating network endows the fabric with excellent breathability while maintaining high strength characteristics. The intelligent self-repair function can automatically repair minor damages and extend the service life of the product. The addition of bioactive ingredients enables the material to have long-term antibacterial ability, ensuring the health and safety of wearing from the source.

[0056] In the present invention, bio-based raw materials and clean processes are adopted throughout the process, avoiding the emission of toxic chemical substances. After being discarded, it can be quickly decomposed naturally without producing microplastic pollution. The energy-saving manufacturing technology greatly reduces production energy consumption, and the waste recycling technology realizes efficient resource recycling. The degradation products of the material can nourish the soil, forming an ecological closed-loop from production, use to recycling, and truly achieving the deep integration of environmental friendliness and sustainable development.

[0057] It should be noted that in this article, relational terms such as first and second are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the term "including" or any other variant thereof is intended to cover non-exclusive inclusion, so that a process, method, article or device including a series of elements not only includes those elements, but also includes other elements not expressly listed, or further includes elements inherent to such process, method, article or device. Without further limitation, an element defined by the statement "including a..." does not exclude the existence of additional identical elements in the process, method, article or device including the said element.

[0058] The above embodiments are only used to illustrate the technical solutions of the present invention, rather than to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that they can still modify the technical solutions recorded in the foregoing embodiments, or perform equivalent replacements for some of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the various embodiments of the present invention.

Claims

1. A radiation-proof and degradable environmentally friendly clothing material, characterized by: The radiation-proof and degradable environmentally friendly clothing materials include: 40 parts of sodium alginate / polylactic acid composite nanofibers, 25 parts of polypyrrole conductive nanofibers, 15 parts of chitin nanocrystals, 10 parts of bismuth tungstate nanosheets, 8 parts of silver nanowire / graphene complexes, 12 parts of corn protein modified coating agents, 7 parts of shark skin-like microgroove structure layers, 5 parts of biological activated carbon nanospheres, 3 parts of natural tannic acid crosslinking agents, and 6 parts of silk fibroin self-repairing emulsions; Among them, bismuth tungstate nanosheets were synthesized by hydrothermal method and have a lamellar structure with exposed crystal faces; the shark skin-like microgroove structure layer was prepared by 3D printing photocuring technology, with a groove depth of 50-80μm; the bioactivated carbon nanospheres were prepared from waste coconut shells by microbial activation method, with a specific surface area of ​​≥2000m 2 / g.

2. The manufacturing process of the radiation-proof and degradable environmentally friendly clothing material according to claim 1, characterized in that: The manufacturing process comprises: S1: Using melt-blowing-electrospinning composite process, sodium alginate / polylactic acid composite nanofibers and polypyrrole conductive fibers are formed into a three-dimensional interpenetrating network structure in an alternating electric field, and the melt temperature is controlled at 185°C and the electric field strength is 25 kV / cm; S2: Depositing bismuth tungstate / graphene composite film on the substrate surface by magnetron sputtering technology, with target power of 300W and argon pressure of 0.8Pa, to form a gradient shielding layer with a thickness of 200nm; S3: using microfluidic chip technology to prepare chitin nanocrystal suspension, and in situ self-assembly with zein modifier in an alkaline environment of pH = 9 to form a nanoscale core-shell structure; S4: Biomimetic microgrooves were constructed on the surface of the material using bio-enzyme etching technology, and immobilized papain was treated at 45 °C for 2 h to form directional fluid channels; S5: Use supercritical CO2 fluid infiltration process to load bio-activated carbon nanospheres, with an operating pressure of 15MPa and a temperature of 40°C to achieve nanoscale pore filling; S6: Activating natural tannic acid by microwave-assisted cross-linking technology, irradiating at a frequency of 2.45 GHz for 90 seconds, initiating an intermolecular condensation reaction to form a three-dimensional cross-linked network; S7: The silk fibroin self-repairing emulsion was deposited by screen printing technology with a patterning accuracy of 50 μm, and a smart responsive repair layer was formed by humidity gradient treatment; S8: low-temperature plasma grafting modification, treatment in a helium / oxygen mixed atmosphere for 10 minutes, the surface energy is reduced to below 20 mN / m; S9: Through bioenzymatic degradation pretreatment, use a lipase / protease complex preparation at 50°C for 30 minutes to activate the biodegradation active points of the material.

3. The radiation-proof and degradable environmentally friendly clothing material and its manufacturing process as claimed in claim 1, characterized in that: In the step S1, a dual-die composite spinning system is used, the left melt-blown die ejects the sodium alginate / polylactic acid complex at a melting temperature of 185±2°C at an extrusion rate of 0.15 g / min, and the right electrospinning device uses an 18G stainless steel needle to spin a DMAC solution containing 3 wt% polypyrrole at a propulsion speed of 1.2 mL / h under the action of a 25 kV / cm alternating electric field; the receiving device uses a copper mesh drum with a rotation speed of 1200 rpm, and the melt-blown fiber and the electrospun fiber intersect at a distance of 20 cm from the die to form a three-dimensional network with a fiber diameter gradient distribution of 200 nm-5 μm; the ambient temperature and humidity are controlled at 25±1°C and 45±5% RH, and the continuous spinning time is maintained for 2.5 hours to obtain a 0.3 mm thick substrate.

4. The radiation-proof, degradable and environmentally friendly clothing material and its manufacturing process as claimed in claim 1, characterized in that: In the step S2, a dual-target magnetron sputtering device is used, and the bismuth tungstate target and the graphene target are placed relative to each other at an angle of 45°; the vacuum degree of the sputtering chamber is maintained at 1×10^-3Pa, and argon gas is introduced to stabilize the working gas pressure at 0.8Pa; 300W RF power is applied to the bismuth tungstate target, 150W DC power is applied to the graphene target, and the substrate table rotates at a constant speed of 5rpm; the deposition process is divided into three stages: the initial 10 minutes are pure bismuth tungstate deposition to form a 20nm bottom layer, the middle 15 minutes are co-sputtering of the two targets to form an 80nm transition layer, and the last 20 minutes are pure graphene deposition to complete a 100nm surface layer; the substrate temperature is maintained at 80±2°C throughout the process, and the deposition rate is controlled at 6.5nm / min.

5. The radiation-proof, degradable and environmentally friendly clothing material and its manufacturing process as claimed in claim 1, characterized in that: In the step S3, a quartz glass microfluidic chip is used, the main channel width is 200 μm, and an acetic acid solution containing 5 wt% chitin nanocrystals and a Tris-HCl buffer containing 8 wt% zein are pumped into the two branches respectively, and the flow rates are set to 15 μL / min and 30 μL / min respectively; the two-phase fluid generates eddy shear in the serpentine mixing channel to trigger the interfacial self-assembly reaction; the collecting device is maintained at a constant temperature of 50° C., and the product is centrifuged at 12000 rpm for 10 minutes to obtain core-shell particles with a diameter of 80-120 nm and a shell thickness of 15 nm.

6. The radiation-proof, degradable and environmentally friendly clothing material and its manufacturing process as claimed in claim 1, characterized in that: In the step S4, the immobilized papain is dispersed in a pH 6.8 phosphate buffer to prepare a 3 wt% enzyme solution; the substrate is immersed in the enzyme solution at 45±0.5° C. for 120 minutes, and a 0.6 T axial magnetic field is applied to guide the enzymatic hydrolysis direction; the treated material is rinsed with deionized water, and then detected by atomic force microscopy to form a parallel groove array with a depth of 65±8 μm and a spacing of 150±20 μm, and the groove surface roughness Ra value reaches 2.3 μm.

7. The radiation-proof, degradable and environmentally friendly clothing material and its manufacturing process as claimed in claim 1, characterized in that: In the step S5, a supercritical reactor with a volume of 5 L is used to pre-disperse the bioactivated carbon nanospheres in ethanol to form a 2 mg / mL suspension; supercritical CO2 is introduced at a flow rate of 12 L / min for 60 minutes under a pressure of 15 MPa and 40° C.; after the infiltration is completed, the pressure is slowly released at a rate of 0.5 MPa / min, and the loading amount of the nanospheres in the pores reaches 23±2 wt%; SEM observation shows that the pore filling rate of 50-200 nm reaches 91%, and the macroporous structure remains intact.

8. The radiation-proof, degradable and environmentally friendly clothing material and its manufacturing process as claimed in claim 1, characterized in that: In the step S6, an ethanol solution containing 5 wt% natural tannic acid is uniformly coated on the surface of the material and placed in a 2450 MHz microwave reactor; the output power is set to 800 W, the irradiation time is 90 seconds, and the peak temperature in the cavity is controlled below 75° C. A three-dimensional network layer with a thickness of about 500 nm is formed on the surface of the cross-linked material, and FTIR detection shows that the characteristic phenolic hydroxyl peak intensity is reduced by 38%, and the cross-linking density is increased to 3.2×10^20bonds / cm 3 .

9. The radiation-proof, degradable and environmentally friendly clothing material and its manufacturing process as claimed in claim 1, characterized in that: In the step S7, a 300-mesh stainless steel screen is used, and the screen pattern is made by ultraviolet photolithography technology with a minimum line width of 50 μm; the viscosity of the silk fibroin emulsion is adjusted to 3500±200 mPa·s, the scraper pressure is set to 0.25 MPa, and printing is performed at a speed of 10 mm / s; the printed material is treated in a 30%→60% step-up humidity environment for 4 hours, and the β-folded structure content in the emulsion is increased from 12% to 47%, forming a smart response layer with a thickness of 8±1 μm.

10. The radiation-proof, degradable and environmentally friendly clothing material and its manufacturing process as claimed in claim 1, characterized in that: In step S8, a mixed gas of helium and oxygen in a volume ratio of 4:1 was introduced into the RF plasma equipment, and the working pressure was maintained at 40 Pa; a 13.56 MHz RF power supply was applied, and the power density was set to 1.5 W / cm 2 The treatment time is strictly controlled within 600 seconds. The surface oxygen content of the treated material is increased from 8.3% to 22.1%. The contact angle test shows that the water contact angle reaches 152° and the rolling angle is less than 5°. In the step S9, a composite enzyme solution containing lipase and protease is prepared, with the mass ratio of enzyme to material being 1:20; the solution is treated in a 50° C. circulating water bath for 30 minutes, and the pH value of the treated solution is automatically stabilized at 7.8±0.2.

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