Nuclear-biochemical multi-effect protective clothing capable of simultaneously protecting neutrons and gamma rays and preparation method of nuclear-biochemical multi-effect protective clothing

Abstract

The invention relates to the technical field of nuclear and biochemical protective clothing, and aims to solve the problem that the existing nuclear protective clothing is difficult to realize multi-dimensional protection effects of radiation protection on gamma rays and neutron rays and protection on biochemical toxic substances at the same time. The nuclear-biochemical multi-effect protective clothing comprises an outer protective layer, a middle shielding layer and an inner skin-friendly layer which are sequentially stacked, the outer protective layer comprises a polymer fiber layer and silicon dioxide polydopamine microspheres embedded in the polymer fiber layer, and the middle shielding layer is arranged between the outer protective layer and the inner skin-friendly layer. The middle shielding layer comprises a boron-containing polyethylene base layer and a gamma shielding coating covering the surface of the boron-containing polyethylene base layer. The nuclear-biological-chemical multi-effect protective garment is of a multi-layer composite structure, all the layers are tightly combined, and the comprehensive protective effect on neutrons, gamma radiation, chemical toxicants and biological warfare agents is cooperatively achieved.

Description

Technical Field

[0001] This invention relates to the field of nuclear, biological, and chemical protective clothing technology, and more specifically, to a multi-effect nuclear, biological, and chemical protective clothing that can simultaneously protect against neutrons and gamma rays, and its preparation method. Background Technology

[0002] In fields such as nuclear energy utilization, nuclear accident emergency response, radiotherapy, and military, personnel face the dual threat of radiation from neutrons and gamma rays. They may also be exposed to hazards such as chemical agents and biological warfare agents. In particular, the use of dirty bombs and depleted uranium bombs in actual combat makes the need for neutron protection even more urgent.

[0003] Traditional nuclear, biological, and chemical (NBC) protective suits have limitations in their protective performance. For radiation protection, most existing suits focus only on a single type of radiation; for example, some suits are designed specifically for gamma rays, using heavy metals like lead for shielding, but they are ineffective against neutron radiation. Neutrons, being uncharged and highly penetrating, can trigger various nuclear reactions, easily causing severe damage to human cells. Currently, existing protective suits cannot effectively protect against both neutrons and gamma rays simultaneously, and they also suffer from problems such as being heavy and lacking flexibility, affecting the wearer's mobility and hindering prolonged work.

[0004] While conventional protective suits may meet certain requirements in terms of chemical and biological protection, their integration with radiation protection is insufficient. There is a lack of integrated protective suits that can effectively protect against neutrons, gamma rays, chemical agents, and biological warfare agents simultaneously. Furthermore, in complex nuclear, biological, and chemical (NBC) environments, protective suits need to possess excellent sealing, comfort, and durability. However, current nuclear protective suits struggle to simultaneously meet the high standards of nuclear protection, NBC protection, sealing, and comfort. Therefore, there is an urgent need for a NBC protective suit with multi-dimensional protective capabilities. Summary of the Invention

[0005] The purpose of this invention is to solve the problem that existing nuclear protective suits are unable to achieve multi-dimensional protection against both gamma rays and neutron rays, as well as against biochemical toxins.

[0006] This invention is achieved through the following technical solution: This invention provides a multi-functional protective suit that can simultaneously protect against neutrons and gamma rays, comprising an outer protective layer, a middle shielding layer, and an inner skin-friendly layer stacked sequentially. The outer protective layer includes a polymer fiber layer and silica polydopamine microspheres embedded in the polymer fiber layer. The middle shielding layer includes a boron-containing polyethylene base layer and a gamma shielding coating applied to the surface of the boron-containing polyethylene base layer.

[0007] Preferably, the outer protective layer has a thickness of 0.5-0.8 mm, the middle shielding layer has a thickness of 2-3.5 mm, and the inner skin-friendly layer has a thickness of 0.5-1 mm.

[0008] Preferably, the total thickness of the nuclear, biological, and chemical multi-effect protective suit is 3-5 mm.

[0009] Preferably, the preparation method of the silica polydopamine microspheres in the outer protective layer includes the following steps: A1 Take silica particles and fluorine modifier, mix them, heat to 70-90℃ under nitrogen protection, react, wash and dry to obtain fluorinated silica; A2. Fluorinated silica is dispersed in a buffer solution, then dopamine hydrochloride is added, and the mixture is stirred to react, thus obtaining silica polydopamine microspheres.

[0010] Preferably, the silica polydopamine microspheres account for 10-20 wt% of the total mass of the outer protective layer.

[0011] Preferably, the method for preparing the intermediate shielding layer includes the following steps: B1 Take boron carbide powder, add coupling agent, dissolve in organic solvent, sonicate, and then dry for later use; B2 takes polyethylene masterbatch, heats and melts it, adds boron carbide powder treated in B1, heats it to 170-180℃, rolls it multiple times, granulates it, and produces boron-containing polyethylene base layer through hot melt spinning. B3. A tungsten or bismuth layer is applied to the surface of a boron-containing polyethylene base layer to obtain an intermediate shielding layer.

[0012] Preferably, in step B2, the mass ratio of polyethylene masterbatch to boron carbide powder is 1:2-4.

[0013] Preferably, in the intermediate shielding layer, the thickness of the tungsten layer or bismuth layer is 5-25% of the thickness of the boron-containing polyethylene base layer.

[0014] Preferably, the method for preparing the inner skin-friendly layer includes the following steps: C1 Take para-aramid and meta-aramid, clean and degrease them respectively, and perform surface activation treatment. Dry them for later use. C2 The para-aramid and meta-aramid obtained in C1 are blended with cotton fibers, and then used as warp and weft yarns respectively to obtain a preliminary fiber layer; then the preliminary fiber layer is immersed in polyethylene glycol or chitosan solution and dried to obtain the inner skin-friendly layer.

[0015] The present invention also provides a method for preparing the above-mentioned multi-effect protective suit that can simultaneously protect against neutrons and gamma rays, comprising the following steps: The outer protective layer, the middle shielding layer, and the inner skin-friendly layer are stacked in sequence and placed in an ultrasonic environment with a frequency of 20-40kHz and an amplitude of 30-50μm. Ultrasonic welding is performed with a pressure of 0.5-1.5MPa, followed by cutting and sewing to obtain the nuclear, biological, and chemical multi-effect protective suit.

[0016] The technical solution of the present invention has the following beneficial effects: The multi-effect protective suit for nuclear, biological and chemical warfare proposed in this invention adopts a multi-layer composite structure, including an outer protective layer, a middle shielding layer and an inner skin-friendly layer. The layers are tightly combined to achieve a comprehensive protective effect against neutrons, gamma radiation, chemical agents and biological warfare agents.

[0017] Specifically, the outer protective layer is formed by electrospinning fluorinated silica polydopamine microspheres into the polymer fiber layer, creating a superhydrophobic outer protective layer that can resist physical contact with chemical and biological agents, significantly reducing their adhesion to the outer material surface or their infiltration, thus effectively isolating biochemical toxins. The middle shielding layer uses boron-containing polyethylene as the base material and is coated with a tungsten or bismuth-containing coating. The hydrogen in the boron-containing polyethylene can slow down neutrons; when a neutron collides with a hydrogen nucleus, its energy decreases. The boron carbide composite in the base material can efficiently absorb the slowed neutrons, capturing them through a reaction, thereby effectively protecting against neutron radiation. The surface coating can block gamma rays and is uniformly dispersed in the base material in the form of powder, particles, or fibers, thus not significantly increasing the weight of the protective clothing material while effectively shielding against gamma rays. The inner skin-friendly layer uses skin-friendly and breathable fiber materials, achieving good shielding protection while also improving the user's wearing comfort. Detailed Implementation

[0018] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. Where specific conditions are not specified in the embodiments, they are performed according to conventional conditions or conditions recommended by the manufacturer; where the manufacturers of the instruments, equipment, reagents, or raw materials used are not specified, they are all conventional products that can be purchased commercially.

[0019] This invention provides a multi-effect protective suit that can simultaneously protect against neutrons and gamma rays. The suit adopts a multi-layer composite structure, including an outer protective layer, a middle shielding layer, and an inner skin-friendly layer. The layers are tightly combined to achieve a comprehensive protective effect against neutrons, gamma radiation, chemical agents, and biological warfare agents.

[0020] In this invention, the multi-effect protective suit for nuclear, biological, and chemical (NBC) applications comprises an outer protective layer, a middle shielding layer, and an inner skin-friendly layer stacked sequentially from the outside to the inside. Adjacent layers are connected by ultrasonic welding, avoiding the problem of adhesive bonding performance deteriorating over time that occurs with adhesive methods. The outer protective layer has a thickness of 0.5-0.8 mm, the middle shielding layer has a thickness of 2-3.5 mm, the inner skin-friendly layer has a thickness of 0.5-1 mm, and the total thickness of the NBC multi-effect protective suit is 3-5 mm.

[0021] The outer protective layer uses polytetrafluoroethylene and polyurethane as base materials to form a polymer fiber layer, which has excellent corrosion resistance and wear resistance, as well as good weather resistance and hydrophobicity. Fluorinated silica polydopamine microspheres (F-SiO2@PDA) are embedded into the polymer fiber layer through electrospinning to form an outer protective layer with a superhydrophobic surface, which can resist physical contact with chemical agents and biological warfare agents, and significantly reduce their adhesion to the surface of the outer material or their inward penetration.

[0022] The preparation method of F-SiO2@PDA in the outer protective layer includes the following steps: (1) Dissolve tetraethyl orthosilicate in an aqueous ethanol solution, add ammonia as a catalyst, heat to 40-60℃, stir for 5-8 hours to generate silica microspheres with controllable particle size of 100-300nm, centrifuge, wash, dry to obtain silica particles for later use.

[0023] (2) Disperse silica particles in anhydrous toluene and sonicate to form a uniform silica suspension; mix silica particles and fluorine modifier at a mass ratio of 1:0.3-0.8, heat to 70-90℃ under nitrogen protection and react for 10-15h to graft fluorocarbon chains onto the silica surface via silane coupling reaction; finally, centrifuge and wash with ethanol or deionized water to remove unreacted reagents, and vacuum dry to obtain fluorinated silica (F-SiO2).

[0024] (3) Disperse F-SiO2 in Tris-HCl buffer solution with pH value of 8.0-9.0 and control the concentration to 1-5 mg / mL; then add dopamine hydrochloride with an equal silicon content, stir and react at room temperature for 24 h. While forming polydopamine, polydopamine forms a uniform coating layer with a thickness of about 20-50 nm on the surface of F-SiO2 through oxidation self-polymerization, thus obtaining F-SiO2@PDA.

[0025] The F-SiO2@PDA prepared by the above method can be applied to the surface of the base material to form a Cassie-Baxter state. F-SiO2 provides low surface energy, which can inhibit the spread of chemical liquids and biological particles on the material surface and reduce the adhesion and infiltration of dust and harmful substances.

[0026] The intermediate shielding layer uses boron-containing polyethylene as the base material and is coated with a tungsten or bismuth-containing coating. The hydrogen in the boron-containing polyethylene can slow down neutrons. When a neutron collides with a hydrogen nucleus, the neutron energy decreases. The boron carbide composite in the base material can efficiently absorb the slowed neutrons and capture them through reaction, thereby effectively protecting against neutron radiation. The coating on the surface can block and shield gamma rays and is uniformly dispersed in the base material in the form of powder, particles or fibers. This means that it does not significantly increase the weight of the protective clothing material, while effectively shielding gamma rays.

[0027] Specifically, the method for preparing the intermediate shielding layer includes the following steps: (1) Take boron carbide powder, heat it to 100-120℃ and dry it; then mix the boron carbide powder with the coupling agent, dissolve it in ethanol solvent, sonicate it for 30 min, and dry it for later use.

[0028] (2) Take polyethylene masterbatch, place it in an open mill, and after it melts, add the above boron carbide powder, antioxidant and a small amount of plasticizer. At 170-180℃, repeatedly roll and press until the mixture is uniform, granulate, and make boron-containing polyethylene base layer by hot melt spinning.

[0029] (3) Take a boron-containing polyethylene base layer and apply a tungsten or bismuth layer to the surface of the boron-containing polyethylene base layer by means of magnetron sputtering or thermal spraying as a gamma shielding coating to obtain an intermediate shielding layer.

[0030] The inner skin-friendly layer is mainly made of aramid fiber, which can be a combination of para-aramid and meta-aramid to form a protective clothing bottom layer that has both strong support and good comfort.

[0031] Specifically, (1) Take para-aramid and meta-aramid, clean them with ethanol or acetone by ultrasonic cleaning to clean and degrease them, then use Ar / O2 mixed gas for plasma treatment, and then place them in sodium hydroxide solution and soak them at 50-80℃ for 0.5-3h. Take them out and dry them for later use.

[0032] (2) Take the para-aramid and meta-aramid obtained after the above treatment, and blend them with cotton fibers at a volume ratio of 3-5:1 to form two kinds of primary spinning, which are used as warp and weft yarns respectively to obtain a primary fiber layer; place the primary fiber layer in polyethylene glycol or chitosan solution for padding, take it out and place it at 120°C for drying to obtain the inner skin-friendly layer.

[0033] In this invention, after each of the above-mentioned material layers is prepared, they are stacked in sequence and subjected to ultrasonic welding for 0.5-1.5 MPa under an ultrasonic environment with a frequency of 20-40 kHz and an amplitude of 30-50 μm. After cutting, sewing and other treatments, a nuclear, biological and chemical multi-effect protective suit that can protect against neutrons and gamma rays is obtained.

[0034] Example 1 Step 1: Dissolve tetraethyl orthosilicate in an ethanol-water solution, then add ammonia for catalysis, heat to 50℃, stir at 120 rpm for 6 hours, then separate the solid and liquid, wash and dry, grind and sieve to obtain SiO2 microspheres with a particle size of 200±20 nm; then disperse the SiO2 microspheres in anhydrous toluene, sonicate for 30 min to obtain a silicon suspension, mix the silicon suspension with perfluorooctyltriethoxysilane at a mass ratio of 1:0.5, heat to 80℃, react for 12 h, then filter out the solid microspheres, wash with ethanol, and vacuum dry to obtain F-SiO2; disperse F-SiO2 in Tris-HCl buffer solution with a pH of 8.5, control the concentration at 2 mg / mL, then add dopamine hydrochloride of equal mass to silicon, stir at 150 rpm for 24 h at room temperature to obtain F-SiO2@PDA with a polydopamine coating. Polytetrafluoroethylene was separately prepared into a polymer fiber layer through melt spinning and blending processes. The fiber layer was then impregnated in a solution containing F-SiO2@PDA, with the mass ratio of F-SiO2@PDA to the polymer fiber layer controlled at 1.5:8. The solution was heated to 60°C and impregnated for 5 hours to obtain an outer protective layer with a thickness of 0.6 mm.

[0035] Step 2: Take boron carbide powder, heat to 120℃ and dry. Then mix the boron carbide powder with KH-550 coupling agent, dissolve in ethanol solvent, sonicate for 30 minutes, and dry for later use. Take polyethylene masterbatch, place it in a two-roll mill, heat until completely melted, add the above-treated boron carbide powder at a mass ratio of 1:2.5, and then add 3wt% of 1010 antioxidant and 0.5wt% of DOP plasticizer based on the total mass of the above materials. Repeated rolling at 75℃ until uniformly mixed, granulated, and then processed into boron-containing polyethylene base layer through hot melt spinning and blending processes; subsequently, bismuth powder, epoxy resin and acetone were mixed and diluted at a mass ratio of 2:3.5:3, and ball-milled for 2 hours to obtain bismuth homogenate. The bismuth homogenate was sprayed onto the surface of the boron-containing polyethylene base layer using an air spray gun with a pressure of 0.35MPa and a distance of 20cm. Then it was baked at 80℃ for 1 hour to obtain an intermediate shielding layer with a thickness of 2.8mm and a bismuth layer on the surface.

[0036] Step 3: Take equal masses of para-aramid and meta-aramid, ultrasonically clean them with ethanol, then treat them with plasma using an equal volume of Ar / O2 mixed gas, and then soak them in a 5% sodium hydroxide solution at 60°C for 1 hour. Remove and dry them for later use. Spin the treated para-aramid and meta-aramid with cotton fibers at a volume ratio of 4:1 to obtain warp and weft yarns, respectively. Then, through warp and weft blending, a preliminary fiber layer is obtained. The preliminary fiber layer is immersed in a polyethylene glycol solution and then dried at 120°C for 2 hours to obtain an inner skin-friendly layer with a thickness of 0.8 mm.

[0037] Step 4: Stack the materials in the order of outer protective layer, middle shielding layer and inner skin-friendly layer, place them in an ultrasonic environment with a frequency of 30kHz and an amplitude of 40μm, apply 1MPa pressure and perform ultrasonic welding for 0.5s to obtain the main fabric of the nuclear, biological and chemical multi-effect protective suit.

[0038] Example 2 Step 1: Dissolve tetraethyl orthosilicate in an ethanol-water solution, then add ammonia for catalysis, heat to 50℃, stir at 120 rpm for 6 hours, then separate the solid and liquid, wash and dry, grind and sieve to obtain SiO2 microspheres with a particle size of 200±20 nm; then disperse the SiO2 microspheres in anhydrous toluene, sonicate for 30 min to obtain a silicon suspension, mix the silicon suspension with perfluorooctyltriethoxysilane at a mass ratio of 1:0.5, heat to 80℃, react for 12 h, then filter out the solid microspheres, wash with ethanol, and vacuum dry to obtain F-SiO2; disperse F-SiO2 in Tris-HCl buffer solution with a pH of 8.5, control the concentration at 2 mg / mL, then add dopamine hydrochloride of equal mass to silicon, stir at 150 rpm for 24 h at room temperature to obtain F-SiO2@PDA with a polydopamine coating. Polytetrafluoroethylene was separately prepared into a polymer fiber layer through melt spinning and blending processes. The fiber layer was then impregnated in a solution containing F-SiO2@PDA, with the mass ratio of F-SiO2@PDA to the polymer fiber layer controlled at 1.5:8. The solution was heated to 60°C and impregnated for 5 hours to obtain an outer protective layer with a thickness of 0.5 mm.

[0039] Step 2: Take boron carbide powder, heat it to 120℃ and dry it. Then mix the boron carbide powder with KH-550 coupling agent, dissolve it in ethanol solvent, sonicate for 30 minutes, and dry it for later use. Take polyethylene masterbatch, place it in a two-roll mill, heat it until completely melted, add the above-treated boron carbide powder according to the mass ratio, and control the mass ratio of polyethylene masterbatch to boron carbide powder to be 1:2.2. Then add 3wt% of 1010 antioxidant and 0.5wt% of DOP plasticizer according to the total mass of the above materials, and repeatedly roll it at 175℃ until it is uniformly mixed. Granulate it, and make boron-containing polyethylene base layer through hot melt spinning and blending process. Then, using tungsten as target material, adjust the temperature to 80℃, the sputtering power to 180W, and the argon pressure to 2 Pa, and coat the surface of boron-containing polyethylene base layer with tungsten coating by magnetron sputtering. Then anneal it at 60℃ for 1 hour to obtain an intermediate shielding layer with a tungsten coating thickness of 3.0mm.

[0040] Step 3: Take equal masses of para-aramid and meta-aramid, ultrasonically clean them with ethanol, then treat them with plasma using an equal volume of Ar / O2 mixed gas, and then soak them in a 5% sodium hydroxide solution at 60°C for 1 hour. Remove and dry them for later use. Spin the treated para-aramid and meta-aramid with cotton fibers at a volume ratio of 4:1 to obtain warp and weft yarns, respectively. Then, through warp and weft blending, a preliminary fiber layer is obtained. The preliminary fiber layer is immersed in a polyethylene glycol solution and then dried at 120°C for 2 hours to obtain an inner skin-friendly layer with a thickness of 0.8 mm.

[0041] Step 4: Stack the materials in the order of outer protective layer, middle shielding layer and inner skin-friendly layer, place them in an ultrasonic environment with a frequency of 30kHz and an amplitude of 40μm, apply 1MPa pressure and perform ultrasonic welding for 0.5s to obtain the main fabric of the nuclear, biological and chemical multi-effect protective suit.

[0042] Example 3 Step 1: Dissolve tetraethyl orthosilicate in an ethanol-water solution, then add ammonia for catalysis, heat to 50℃, stir at 120 rpm for 6 hours, then separate the solid and liquid, wash and dry, grind and sieve to obtain SiO2 microspheres with a particle size of 200±20 nm; then disperse the SiO2 microspheres in anhydrous toluene, sonicate for 30 min to obtain a silicon suspension, mix the silicon suspension with perfluorooctyltriethoxysilane at a mass ratio of 1:0.5, heat to 80℃, react for 12 h, then filter out the solid microspheres, wash with ethanol, and vacuum dry to obtain F-SiO2; disperse F-SiO2 in Tris-HCl buffer solution with a pH of 8.5, control the concentration at 2 mg / mL, then add dopamine hydrochloride of equal mass to silicon, stir at 150 rpm for 24 h at room temperature to obtain F-SiO2@PDA with a polydopamine coating. Polytetrafluoroethylene was separately prepared into a polymer fiber layer through melt spinning and blending processes. The fiber layer was then impregnated in a solution containing F-SiO2@PDA, with the mass ratio of F-SiO2@PDA to the polymer fiber layer controlled at 1:8.5. The solution was heated to 60°C and impregnated for 5 hours to obtain an outer protective layer with a thickness of 0.8 mm.

[0043] Step 2: Take boron carbide powder, heat to 120℃ and dry. Then mix the boron carbide powder with KH-550 coupling agent, dissolve in ethanol solvent, sonicate for 30 minutes, and dry for later use. Take polyethylene masterbatch, place it in a two-roll mill, heat until completely melted, add the above-treated boron carbide powder at a mass ratio of 1:2.5, and then add 3wt% of 1010 antioxidant and 0.5wt% of DOP plasticizer based on the total mass of the above materials. Repeated rolling at 75℃ until uniformly mixed, granulated, and then processed into boron-containing polyethylene base layer through hot melt spinning and blending processes; subsequently, bismuth powder, epoxy resin and acetone were mixed and diluted at a mass ratio of 2:3.5:3, and ball-milled for 2 hours to obtain bismuth homogenate. The bismuth homogenate was sprayed onto the surface of the boron-containing polyethylene base layer using an air spray gun with a pressure of 0.35MPa and a distance of 20cm. Then it was baked at 80℃ for 1 hour to obtain an intermediate shielding layer with a thickness of 2.8mm and a bismuth layer on the surface.

[0044] Step 3: Take equal masses of para-aramid and meta-aramid, ultrasonically clean them with ethanol, then treat them with plasma using an equal volume of Ar / O2 mixed gas, and then soak them in a 5% sodium hydroxide solution at 60°C for 1 hour. Remove and dry them for later use. Spin the treated para-aramid and meta-aramid with cotton fibers at a volume ratio of 4:1 to obtain warp and weft yarns, respectively. Then, through warp and weft blending, a preliminary fiber layer is obtained. The preliminary fiber layer is immersed in a polyethylene glycol solution and then dried at 120°C for 2 hours to obtain an inner skin-friendly layer with a thickness of 0.5 mm.

[0045] Step 4: Stack the materials in the order of outer protective layer, middle shielding layer and inner skin-friendly layer, place them in an ultrasonic environment with a frequency of 30kHz and an amplitude of 40μm, apply 1MPa pressure and perform ultrasonic welding for 0.5s to obtain the main fabric of the nuclear, biological and chemical multi-effect protective suit.

[0046] Comparative Example 1 Step 1: Dissolve tetraethyl orthosilicate in an ethanol-water solution, then add ammonia for catalysis, heat to 50℃, stir at 120 rpm for 6 hours, then separate the solid and liquid, wash and dry, grind and sieve to obtain SiO2 microspheres with a particle size of 200±20 nm; then disperse the SiO2 microspheres in anhydrous toluene, sonicate for 30 min to obtain a silicon suspension, mix the silicon suspension with perfluorooctyltriethoxysilane at a mass ratio of 1:0.5, heat to 80℃, react for 12 h, then filter out the solid microspheres, wash with ethanol, and vacuum dry to obtain F-SiO2; disperse F-SiO2 in Tris-HCl buffer solution with a pH of 8.5, control the concentration at 2 mg / mL, then add dopamine hydrochloride of equal mass to silicon, stir at 150 rpm for 24 h at room temperature to obtain F-SiO2@PDA with a polydopamine coating. Polytetrafluoroethylene was separately prepared into a polymer fiber layer through melt spinning and blending processes. The fiber layer was then impregnated in a solution containing F-SiO2@PDA, with the mass ratio of F-SiO2@PDA to the polymer fiber layer controlled at 1.5:8. The solution was heated to 60°C and impregnated for 5 hours to obtain an outer protective layer with a thickness of 0.6 mm.

[0047] Step 2: Take equal masses of para-aramid and meta-aramid, ultrasonically clean them with ethanol, then treat them with plasma using an equal volume of Ar / O2 mixed gas, and then soak them in a 5% sodium hydroxide solution at 60°C for 1 hour. Remove and dry them for later use. Spin the treated para-aramid and meta-aramid with cotton fibers at a volume ratio of 4:1 to obtain warp and weft yarns, respectively. Then, through warp and weft blending, a preliminary fiber layer is obtained. The preliminary fiber layer is immersed in a polyethylene glycol solution and then dried at 120°C for 2 hours to obtain an inner skin-friendly layer with a thickness of 0.8 mm.

[0048] Step 3: Stack the outer protective layer and the inner skin-friendly layer, place them in an ultrasonic environment with a frequency of 30kHz and an amplitude of 40μm, apply a pressure of 1MPa, and perform ultrasonic welding for 0.5s to obtain the main fabric of the nuclear, biological and chemical multi-effect protective suit.

[0049] Comparative Example 2 Step 1: Take boron carbide powder, heat to 120℃ and dry. Then mix the boron carbide powder with KH-550 coupling agent, dissolve in ethanol solvent, sonicate for 30 minutes, and dry for later use. Take polyethylene masterbatch, place it in a two-roll mill, heat until completely melted, add the above-treated boron carbide powder at a mass ratio of 1:2.5, and then add 3wt% of 1010 antioxidant and 0.5wt% of DOP plasticizer based on the total mass of the above materials. Repeated rolling at 175℃ until uniformly mixed, granulated, and then processed into boron-containing polyethylene base layer through hot melt spinning and blending processes; subsequently, bismuth powder, epoxy resin and acetone were mixed and diluted at a mass ratio of 2:3.5:3, and ball-milled for 2 hours to obtain bismuth homogenate. The bismuth homogenate was sprayed onto the surface of the boron-containing polyethylene base layer using an air spray gun with a pressure of 0.35MPa and a distance of 20cm. Then it was baked at 80℃ for 1 hour to obtain a shielding layer with a thickness of 2.8mm and a bismuth layer on the surface.

[0050] Step 2: Take equal masses of para-aramid and meta-aramid, ultrasonically clean them with ethanol, then treat them with plasma using an equal volume of Ar / O2 mixed gas, and then soak them in a 5% sodium hydroxide solution at 60°C for 1 hour. Remove and dry them for later use. Spin the treated para-aramid and meta-aramid with cotton fibers at a volume ratio of 4:1 to obtain warp and weft yarns, respectively. Then, through warp and weft blending, a preliminary fiber layer is obtained. The preliminary fiber layer is immersed in a polyethylene glycol solution and then dried at 120°C for 2 hours to obtain an inner skin-friendly layer with a thickness of 0.8 mm.

[0051] Step 3: Stack the shielding layer and the inner skin-friendly layer, place them in an ultrasonic environment with a frequency of 30kHz and an amplitude of 40μm, apply a pressure of 1MPa, and perform ultrasonic welding for 0.5s to obtain the main fabric of the nuclear, biological and chemical multi-effect protective suit.

[0052] Comparative Example 3 Step 1: Dissolve tetraethyl orthosilicate in an ethanol-water solution, then add ammonia for catalysis, heat to 50℃, stir at 120 rpm for 6 hours, then separate the solid and liquid, wash and dry, grind and sieve to obtain SiO2 microspheres with a particle size of 200±20 nm; then disperse the SiO2 microspheres in anhydrous toluene, sonicate for 30 min to obtain a silicon suspension, mix the silicon suspension with perfluorooctyltriethoxysilane at a mass ratio of 1:0.5, heat to 80℃, react for 12 h, then filter out the solid microspheres, wash with ethanol, and vacuum dry to obtain F-SiO2; disperse F-SiO2 in Tris-HCl buffer solution with a pH of 8.5, control the concentration at 2 mg / mL, then add dopamine hydrochloride of equal mass to silicon, stir at 150 rpm for 24 h at room temperature to obtain F-SiO2@PDA with a polydopamine coating. Polytetrafluoroethylene was separately prepared into a polymer fiber layer through melt spinning and blending processes. The fiber layer was then impregnated in a solution containing F-SiO2@PDA, with the mass ratio of F-SiO2@PDA to the polymer fiber layer controlled at 1.5:8. The solution was heated to 60°C and impregnated for 5 hours to obtain an outer protective layer with a thickness of 0.2 mm.

[0053] Step 2: Take boron carbide powder, heat it to 120℃ and dry it. Then mix the boron carbide powder with KH-550 coupling agent, dissolve it in ethanol solvent, sonicate it for 30 minutes, and dry it for later use. Take polyethylene masterbatch, place it in a two-roll mill, heat it until it is completely melted, add the above-treated boron carbide powder according to the mass ratio, and control the mass ratio of polyethylene masterbatch to boron carbide powder to be 1:2.5. Then add 3wt% of 1010 antioxidant and 0.5wt% of DOP plasticizer according to the total mass of the above materials, and repeatedly roll it at 175℃ until it is mixed evenly. Granulate it, and make an intermediate shielding layer with a thickness of about 3mm by hot melt spinning and blending process.

[0054] Step 3: Take equal masses of para-aramid and meta-aramid, ultrasonically clean them with ethanol, then treat them with plasma using an equal volume of Ar / O2 mixed gas, and then soak them in a 5% sodium hydroxide solution at 60°C for 1 hour. Remove and dry them for later use. Spin the treated para-aramid and meta-aramid with cotton fibers at a volume ratio of 4:1 to obtain warp and weft yarns, respectively. Then, through warp and weft blending, a preliminary fiber layer is obtained. The preliminary fiber layer is immersed in a polyethylene glycol solution and then dried at 120°C for 2 hours to obtain an inner skin-friendly layer with a thickness of 0.8 mm.

[0055] Step 4: Stack the materials in the order of outer protective layer, middle shielding layer and inner skin-friendly layer, place them in an ultrasonic environment with a frequency of 30kHz and an amplitude of 40μm, apply 1MPa pressure and perform ultrasonic welding for 0.5s to obtain the main fabric of the nuclear, biological and chemical multi-effect protective suit.

[0056] Comparative Example 4 Step 1: Take polytetrafluoroethylene and make a polymer fiber layer through melt spinning and blending processes. Then, immerse it in a tetraethyl orthosilicate solution, controlling the mass ratio of tetraethyl orthosilicate to polymer fiber layer to be 1.5:8. Heat to 60℃ and immerse for 5 hours to obtain an outer protective layer with a thickness of 0.6 mm.

[0057] Step 2: Take boron carbide powder, heat to 120℃ and dry. Then mix the boron carbide powder with KH-550 coupling agent, dissolve in ethanol solvent, sonicate for 30 minutes, and dry for later use. Take polyethylene masterbatch, place it in a two-roll mill, heat until completely melted, add the above-treated boron carbide powder at a mass ratio of 1:2.5, and then add 3wt% of 1010 antioxidant and 0.5wt% of DOP plasticizer based on the total mass of the above materials. Repeated rolling at 75℃ until uniformly mixed, granulated, and then processed into boron-containing polyethylene base layer through hot melt spinning and blending processes; subsequently, bismuth powder, epoxy resin and acetone were mixed and diluted at a mass ratio of 2:3.5:3, and ball-milled for 2 hours to obtain bismuth homogenate. The bismuth homogenate was sprayed onto the surface of the boron-containing polyethylene base layer using an air spray gun with a pressure of 0.35MPa and a distance of 20cm. Then it was baked at 80℃ for 1 hour to obtain an intermediate shielding layer with a thickness of 2.8mm and a bismuth layer on the surface.

[0058] Step 3: Take equal masses of para-aramid and meta-aramid, ultrasonically clean them with ethanol, then treat them with plasma using an equal volume of Ar / O2 mixed gas, and then soak them in a 5% sodium hydroxide solution at 60°C for 1 hour. Remove and dry them for later use. Spin the treated para-aramid and meta-aramid with cotton fibers at a volume ratio of 4:1 to obtain warp and weft yarns, respectively. Then, through warp and weft blending, a preliminary fiber layer is obtained. The preliminary fiber layer is immersed in a polyethylene glycol solution and then dried at 120°C for 2 hours to obtain an inner skin-friendly layer with a thickness of 0.8 mm.

[0059] Step 4: Stack the materials in the order of outer protective layer, middle shielding layer and inner skin-friendly layer, place them in an ultrasonic environment with a frequency of 30kHz and an amplitude of 40μm, apply 1MPa pressure and perform ultrasonic welding for 0.5s to obtain the main fabric of the nuclear, biological and chemical multi-effect protective suit.

[0060] Comparative Example 5 Step 1: Dissolve tetraethyl orthosilicate in an ethanol-water solution, then add ammonia for catalysis, heat to 50℃, stir at 120 rpm for 6 hours, then separate the solid and liquid, wash and dry, grind and sieve to obtain SiO2 microspheres with a particle size of 200±20 nm; then disperse the SiO2 microspheres in anhydrous toluene, sonicate for 30 min to obtain a silicon suspension, mix the silicon suspension with perfluorooctyltriethoxysilane at a mass ratio of 1:0.5, heat to 80℃, react for 12 h, then filter out the solid microspheres, wash with ethanol, and vacuum dry to obtain F-SiO2; disperse F-SiO2 in Tris-HCl buffer solution with a pH of 8.5, control the concentration at 2 mg / mL, then add dopamine hydrochloride of equal mass to silicon, stir at 150 rpm for 24 h at room temperature to obtain F-SiO2@PDA with a polydopamine coating. Polytetrafluoroethylene was separately prepared into a polymer fiber layer through melt spinning and blending processes. The fiber layer was then impregnated in a solution containing F-SiO2@PDA, with the mass ratio of F-SiO2@PDA to the polymer fiber layer controlled at 1.5:8. The solution was heated to 60°C and impregnated for 5 hours to obtain an outer protective layer with a thickness of 0.6 mm.

[0061] Step 2: Take polyethylene masterbatch, place it in an open mill, heat it until completely melted, add 3 wt% of 1010 antioxidant and 0.5 wt% of DOP plasticizer according to the above material mass, and repeatedly roll it at 175°C until it is evenly mixed. Granulate it, and make a 3 mm thick polyethylene intermediate shielding layer through hot melt spinning and blending processes.

[0062] Step 3: Take equal masses of para-aramid and meta-aramid, ultrasonically clean them with ethanol, then treat them with plasma using an equal volume of Ar / O2 mixed gas, and then soak them in a 5% sodium hydroxide solution at 60°C for 1 hour. Remove and dry them for later use. Spin the treated para-aramid and meta-aramid with cotton fibers at a volume ratio of 4:1 to obtain warp and weft yarns, respectively. Then, through warp and weft blending, a preliminary fiber layer is obtained. The preliminary fiber layer is immersed in a polyethylene glycol solution and then dried at 120°C for 2 hours to obtain an inner skin-friendly layer with a thickness of 0.8 mm.

[0063] Step 4: Stack the materials in the order of outer protective layer, middle shielding layer and inner skin-friendly layer, place them in an ultrasonic environment with a frequency of 30kHz and an amplitude of 40μm, apply 1MPa pressure and perform ultrasonic welding for 0.5s to obtain the main fabric of the nuclear, biological and chemical multi-effect protective suit.

[0064] Test case Samples: Protective clothing main fabrics prepared in Examples 1-3 and Comparative Examples 1-5 (1) Take the above samples respectively and conduct nuclear radiation shielding performance tests. Specifically, according to ISO 14152-2001 "Neutron radiation protection shielding", Am-Be source was used to simulate fast neutrons and detect thermal neutron flux attenuation; then according to ASTM C1831 "Standard Guide for Testing Gamma Radiation Shielding Performance", Cs-137 was used to test the shielding efficiency of secondary gamma rays. The test results are shown in Table 1 below: Table 1. Test results of nuclear radiation shielding performance of different samples

[0065] (2) Take another sample as an example, and measure its tensile strength and other mechanical properties, as well as its biochemical protective properties. The results are shown in Table 2 below: Table 2 Mechanical property test results of different samples

[0066] (3) Take the main body fabric of the protective clothing prepared in Examples 1 to 3 respectively, and determine the interlayer peel strength and bending fatigue resistance of the main body fabric of the nuclear, biological and chemical multi-effect protective clothing made of multi-layer materials in the above examples according to ASTM D903-98 "Standard Test Method for Peel Strength of Adhesives". The test results are shown in Table 3 below: Table 2. Material performance test results of the multi-effect protective suits for nuclear, biological, and chemical (NBC) applications in Examples 1 to 3.

[0067] The above experiments show that the main fabric of the multi-effect nuclear, biological, and chemical protective suit prepared in Examples 1 to 3 exhibits excellent protective performance in both shielding neutron rays and gamma rays. Furthermore, the anti-toxic penetration rate and static contact angle also reflect that this main fabric effectively isolates biochemical toxic substances. It also demonstrates good overall mechanical advantages in terms of interlayer bonding strength and tensile strength. Therefore, it can be concluded that the multi-effect nuclear, biological, and chemical protective suit of the present invention can simultaneously achieve shielding and protection against neutrons and gamma rays, while isolating physical contact with biochemical toxic substances, and possesses good tensile and abrasion resistance. It can be effectively applied in practical nuclear, biological, and chemical protection, achieving more comprehensive and significant protective effects.

[0068] The above are merely preferred embodiments of the present invention and are not intended to limit the present invention. Various modifications and variations can be made to the present invention by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A multi-functional protective suit capable of simultaneously protecting against neutrons and gamma rays, characterized in that, It includes an outer protective layer, an intermediate shielding layer and an inner skin-friendly layer stacked in sequence. The outer protective layer includes a polymer fiber layer and silica polydopamine microspheres embedded in the polymer fiber layer. The intermediate shielding layer includes a boron-containing polyethylene base layer and a gamma shielding coating applied to the surface of the boron-containing polyethylene base layer.

2. The multi-functional protective suit for nuclear, biological, and chemical warfare (NBT) protection against neutrons and gamma rays as described in claim 1, characterized in that, The outer protective layer has a thickness of 0.5-0.8 mm, the middle shielding layer has a thickness of 2-3.5 mm, and the inner skin-friendly layer has a thickness of 0.5-1 mm.

3. The multi-functional protective suit for nuclear, biological, and chemical warfare (NBT) protection against neutrons and gamma rays as described in claim 2, characterized in that, The total thickness of the nuclear, biological, and chemical multi-effect protective suit is 3-5 mm.

4. The multi-functional protective suit for nuclear, biological, and chemical warfare (NBT) protection against neutrons and gamma rays as described in claim 1, characterized in that, The preparation method of the silica polydopamine microspheres in the outer protective layer includes the following steps: A1 Take silica particles and fluorine modifier, mix them, heat to 70-90℃ under nitrogen protection, react, wash and dry to obtain fluorinated silica; A2. Fluorinated silica is dispersed in a buffer solution, then dopamine hydrochloride is added, and the mixture is stirred to react, thus obtaining silica polydopamine microspheres.

5. The multi-functional protective suit for nuclear, biological, and chemical warfare (NBT) protection against neutrons and gamma rays as described in claim 1, characterized in that, The silica polydopamine microspheres account for 10-20 wt% of the total mass of the outer protective layer.

6. The multi-functional protective suit for nuclear, biological, and chemical warfare (NBT) protection against neutrons and gamma rays as described in claim 1, characterized in that, The method for preparing the intermediate shielding layer includes the following steps: B1 Take boron carbide powder, add coupling agent, dissolve in organic solvent, sonicate, and then dry for later use; B2 takes polyethylene masterbatch, heats and melts it, adds boron carbide powder treated in B1, heats it to 170-180℃, rolls it multiple times, granulates it, and produces boron-containing polyethylene base layer through hot melt spinning. B3. A tungsten or bismuth layer is applied to the surface of a boron-containing polyethylene base layer to obtain an intermediate shielding layer.

7. The multi-functional protective suit for nuclear, biological, and chemical warfare (NBT) protection against neutrons and gamma rays as described in claim 6, characterized in that, In step B2, the mass ratio of polyethylene masterbatch to boron carbide powder is 1:2-4.

8. The multi-functional protective suit for nuclear, biological, and chemical warfare (NBT) protection against neutrons and gamma rays as described in claim 6, characterized in that, In the intermediate shielding layer, the thickness of the tungsten or bismuth layer is 5-25% of the thickness of the boron-containing polyethylene base layer.

9. The multi-functional protective suit for nuclear, biological, and chemical warfare (NBT) protection against neutrons and gamma rays as described in claim 1, characterized in that, The method for preparing the inner skin-friendly layer includes the following steps: C1 Take para-aramid and meta-aramid, clean and degrease them respectively, and perform surface activation treatment. Dry them for later use. C2 The para-aramid and meta-aramid obtained in C1 are blended with cotton fibers, and then used as warp and weft yarns respectively to obtain a preliminary fiber layer; then the preliminary fiber layer is immersed in polyethylene glycol or chitosan solution and dried to obtain the inner skin-friendly layer.

10. A method for preparing a multi-functional protective suit for nuclear, biological, and chemical warfare as described in any one of claims 1 to 9, characterized in that, Includes the following steps: The outer protective layer, the middle shielding layer, and the inner skin-friendly layer are stacked in sequence and placed in an ultrasonic environment with a frequency of 20-40kHz and an amplitude of 30-50μm. Ultrasonic welding is performed with a pressure of 0.5-1.5MPa, followed by cutting and sewing to obtain the nuclear, biological, and chemical multi-effect protective suit.

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