KR102454494B1 - Explosion-proof and shock-proof multi-stage heterogeneous fiber preform composite material and manufacturing method thereof - Google Patents

Abstract

The present invention provides an explosion-proof and shock-proof composite material having a significant negative Poisson's ratio effect and a method for manufacturing the same. The explosion-proof and impact-proof composite material includes a substrate and an explosion-proof and impact-proof coating layer covered on the substrate. The explosion-proof and impact-proof coating layer is formed by curing a paint coated on a substrate; The explosion-proof and impact-proof coating layer is provided with a multi-stage heterogeneous fiber preform arranged in parallel in several layers. The projection angle of the multistage heterogeneous fiber preforms between the multistage heterogeneous fiber preforms in each adjacent layer is 5° to 90°. ° to 90 °. The layer spacing of the adjacent multi-stage heterogeneous fiber preforms is between 2 mm and 20 mm. The explosion-proof and shock-proof composite material has greatly improved damping performance, tear resistance performance, tensile performance, energy consumption and energy absorption performance, and can effectively prevent fragmentation due to material damage, and secondary damage to personnel and structures. damage can be reduced.

Description

Explosion-proof and shock-proof multi-stage heterogeneous fiber preform composite material and manufacturing method thereof

The present invention belongs to the field of materials, and relates to an explosion-proof and impact-proof composite material and a method for manufacturing the same, and more particularly, to an explosion-proof and impact-proof composite material based on a multi-stage heterogeneous fiber preform and a method for manufacturing the same.

In recent years, explosion accidents have occurred frequently at home and abroad, posing a serious threat to buildings, facilities, and human life and property. The reason that explosion accidents cause huge loss of life and property is mainly because the occurrence time is short and the impact load is very large, so it is difficult to prepare effective countermeasures to reduce damage. In general, when an explosion occurs, the energy shock first damages units around the center of the explosion; High-speed fragments and shock waves generated by the next explosion cause greater damage to surrounding structures and equipment. Correspondingly, most of the exterior surfaces of current buildings and facilities have only waterproof, anti-corrosive, and fire-proof performance, but it is rarely reported that they have explosion-proof and shock-proof performance. can As can be seen from this, research on explosion-proof and shock-proof composite materials and applying them to buildings and facilities greatly reduces losses from explosion accidents and has important social and economic implications.

Currently, most of the performance, such as waterproofing, anti-corrosion, and fire protection of the outer layers of buildings and facilities, is realized by spraying a coating layer having reactive performance on the matrix structure of buildings and facilities. There have been no reports of explosion-proof and shock-proof coatings on the outer layers of buildings and equipment. However, the patent application 201810482655.5 disclosed "Underwater explosion impact protection coating layer material, manufacturing method and its application". The above application prepares two components, A and B, respectively, mixes A and B components using a two-component high temperature and high pressure impact mixing airless spray machine, and then sprays them on the primer on the surface of the hull to form an underwater explosion impact protection coating layer. . The coating layer according to the above application is currently commonly used in the field of polyurea materials having an explosion-proof function, and the structural design of the fiber reinforcement of the system and its matrix material is relatively traditional, so its glass transition temperature range is narrow and explosion-proof and anti-explosion The improvement in impact performance is limited.

Studying from the material aspect, it is to improve the protection and explosion-proof performance of building and equipment structural materials, to develop buildings and equipment in the direction of high toughness and high ductility, and further improve the explosion-proof local damage performance of the structure; At present, a common means is to add a fiber material with good toughness to the protective coating layer of buildings and equipment to change the low toughness strength and low temperature brittle state of the coating layer to form a new composite material. However, the random distribution of fibers in the coating layer is very limited in improving the impact resistance performance of specific directions and internal structures of buildings and equipment.

For the problems existing in the explosion-proof and shock-proof aspects of buildings and equipment in the prior art, the present invention provides an explosion-proof and shock-proof composite material having a significant negative Poisson's ratio effect, and a method for manufacturing the same. The explosion-proof and shock-proof composite material is greatly improved in damping performance, tear resistance performance, tensile resistance performance, energy consumption and energy absorption performance, and can effectively prevent fragmentation due to material damage, and can effectively prevent fragmentation of personnel and structures. It can reduce car damage.

The technical solution of the present invention is as follows.

The explosion-proof and shock-proof composite material includes a substrate and an explosion-proof and shock-proof coating layer covered on the substrate. The substrate is one or more of metal, ceramic, concrete, glass, polymer and composite material. The explosion-proof and shock-proof coating layer is formed by curing a paint coated on a substrate, and the paint is an alkyd resin, an acrylic resin, an epoxy resin, which is sufficiently dispersed by adding graphene hydroxide. , at least one of phenolic resin, urea-formaldehyde resin, organicsilicone resin, polyurethane, and polyurea; The weight fraction of graphane hydroxide in the paint is 0.2% to 2.0%. The hydroxyl group of graphene hydroxide restricts the movement of molecules through chemical reaction or polar adsorption with the raw material of the coating layer, and increases the phase delay between stress and strain; Therefore, the glass transition temperature region of the coating layer is remarkably widened, the loss modulus and damping performance are greatly improved, the flexibility of the coating layer can be ensured even at low temperatures, the cracking of the coating layer can be prevented, and the low-temperature brittleness of the coating layer can be solved. The explosion-proof and impact-proof coating layer is provided with a multi-stage heterogeneous fiber preform arranged in parallel in several layers. The projection angle of the multistage heterogeneous fiber preforms between the multistage heterogeneous fiber preforms in each adjacent layer is 5° to 90°. ° to 90 °. The layer spacing of the adjacent multi-stage heterogeneous fiber preforms is between 2 mm and 20 mm. The material coated with the explosion-proof and shock-proof coating layer absorbs more energy in the event of an explosion due to the negative Poisson's ratio mesh structure of the multi-stage fiber preform, maintains the integrity of the coating layer, and greatly improves its explosion-proof and shock-proof effect; In addition, it is possible to prevent the flying of fragments due to the explosion at the same impact load, and the degree of secondary damage can be greatly reduced.

the fiber preform is formed by plain weave with warp and weft yarns by a plurality of multi-stage heterogeneous fibers; The multi-stage heterogeneous fibers are wound around the core fiber by the multi-stage auxiliary fibers. The core fiber is a low modulus fiber, and the multi-stage auxiliary fiber is a high modulus fiber having different elastic modulus. The distance between the core fibers of the adjacent multi-stage heterogeneous fibers is between 2 mm and 50 mm. the modulus of elasticity of the low modulus fiber is 50 MPa to 50 GPa; The modulus of elasticity of the high modulus fiber is ≧50 GPa. The auxiliary fiber is wound on the core fiber by dividing the stage; the modulus of elasticity of the first stage auxiliary fiber is 50 GPa to 90 GPa; the elastic modulus ratio of the N-th stage auxiliary fiber to the N-1 stage auxiliary fiber is 1.1 to 9.6, and N is 2 to 7; The diameter ratio of the core fiber to the first stage auxiliary fiber is 1.5 to 3.0, the diameter ratio of the N-th stage auxiliary fiber to the diameter of the N-1 stage auxiliary fiber is 0.5 to 0.9, and the diameter ratio is from 2.5 to 15.0, and N is from 2 to 7; The helix angle of the first stage auxiliary fiber is 2 ° to 8 °, the helix angle of the N-th stage auxiliary fiber is increased by 3 ° to 15 ° compared to the N-1 stage auxiliary fiber, and the helix of the N-th stage auxiliary fiber is The angle is between 5° and 60°, and N is between 2 and 7. The auxiliary fiber uses a multi-stage high modulus fiber in which the spiral angle and the elastic modulus are distributed in a gradient, has excellent durability and high tensile strength, suppresses crack expansion when microcracks occur, and promotes uniform distribution of internal stress in the coating layer Thus, it is possible to improve the compressive strength and impact-proof performance of the coating layer. The flexibility of the low modulus fiber as a core fiber can improve the tensile, flexural, and shear performance of the fiber mesh fabric structure and composite material, and it can sufficiently exert its action when macroscopic cracks occur to prevent rapid damage to the matrix.

Here, the low modulus fiber is a polyethylene fiber, a polyvinyl alcohol fiber, a polyvinyl formal fiber, a polyvinyl chloride fiber, and a polypropylene fiber. fiber), polyacrylonitrile fiber, polyamide fiber, polyimide fiber, polyester fiber, polyurethane fiber, cellulose fiber ), at least one of polytetrafluoroethylene fibers and polyphenylene sulfide fibers; The high modulus fiber is an aramid fiber, polybenzimidazole fiber, polybenzodioxazole fiber, polyarylate fiber, ultra-high molecular weight polyethylene fiber, glass fiber ( glass fiber, carbon fiber, steel fiber, continuous basalt fiber, silicon carbide fiber, magnesium oxide fiber, aluminum oxide fiber (alu) at least one of minium oxide fiber, silica fiber, quartz fiber, aluminum silicate fiber, graphene fiber, and boron fiber.

Preferably, the elastic modulus ratio of the N-th stage auxiliary fiber to the N-1 stage auxiliary fiber is 1.1 to 7.5, and N is 2 to 7; The diameter ratio of the core fiber to the first stage auxiliary fiber is 1.5 to 2.5, the diameter ratio of the core fiber to the Nth stage auxiliary fiber is 2.5 to 10.0, and the helix angle of the Nth stage auxiliary fiber is 10 ° to 60 °, N is 2 to 7.

In the manufacturing method of the explosion-proof and shock-proof composite material, the specific manufacturing method is as follows.

(1) Processing manufacturing step of single-stage heterogeneous fiber embryonic structure: According to the spiral angle of the single-stage structure, the high-modulus fiber, which is a first-stage auxiliary fiber, is wound around a low-modulus fiber, which is a core fiber, to form a single-stage heterogeneous fiber embryo structure get

(2) step of curing treatment of single-stage heterogeneous fiber embryo structure: a curing agent is added to the epoxy resin and stirred sufficiently, wherein the mass ratio of the curing agent to the epoxy resin is 1.0:0.8 to 1.0:1.2; Then, the single-stage heterogeneous fiber embryonic structure prepared in step (1) is immersed, heated to 50° C. to 80° C. to sufficiently immerse the single-stage heterogeneous fiber embryonic structure, and then the hardening system is taken out, and left to stand until hardened. Only heterogeneous fibrous structures are obtained.

(3) Process manufacturing step of multi-stage heterogeneous fiber structure: using the heterogeneous fibers obtained in step (2) as a single-stage structure, and sequentially performing steps (1) and (2) according to the helix angle of the N-stage structure Overlapping to obtain an N-stage heterogeneous fiber structure, N is 2 to 7.

(4) Weaving manufacturing step of multi-stage heterogeneous fiber preform: After weaving the obtained N-stage heterogeneous fibers into warp and weft plain weave structures by warp and weft plain weaving methods along the warp and weft direction, the curing system according to step (2) is subjected to warp and weft All warp and weft intersections of the plain weave structure are sufficiently coated and left to stand until cured to obtain an N-stage heterogeneous fiber preform, where N is 2 to 7.

(5) manufacturing step of explosion-proof and impact-proof composite material: adding graphene hydroxide having a mass fraction of 0.2% to 2.0% to a paint, and sufficiently dispersing it by ultrasonic dispersion to obtain and stockpile a modified paint; disposing one layer of multi-stage heterogeneous fiber preform on the surface of the substrate, and pouring, coating, or spraying the modified paint of 2 mm to 20 mm on the surface of the substrate to cure; Then, the above steps are repeated to obtain the explosion-proof and shock-proof composite material.

Here, the epoxy resin according to step (2) is a bisphenol A epoxy resin; The curing agent is at least one of polyamide, polyester resin, and an aliphatic a mine-based curing agent. The coating layer used for the explosion-proof and impact-proof composite material manufactured according to the above method implements explosion-proof and impact-proof effects in addition to the performance of the general coating layer such as waterproofing, anti-corrosion, and decoration, and by reducing the damage of explosion and impact to the structure, the structure improve the protective performance of This is because the negative Poisson's ratio effect of the multi-stage heterogeneous fiber preform was exhibited to the maximum limit in the composite material, and the explosion-proof and shock-proof ability was improved. In addition, the coating layer can be combined with various substrates and has a wide application range, and the application of explosion-proof and impact-proof materials has important social meaning.

Explosion-proof and shock-proof principle: When a multi-stage heterogeneous fiber preform is subjected to an impact from a non-parallel external force, the auxiliary fibers of each stage of the preform tend to be in a straight state because the modulus of elasticity is relatively high and the elongation at break is relatively low. ; Core fibers tend to become helical because of their relatively low modulus of elasticity and relatively large changes in elongation. Here, the diameter of the core fiber is larger than the diameter of the auxiliary fiber, and under the action of stress, the helical fiber structure broadens in the transverse direction, while the fiber preform shows that the pores of the lattice shrink in the theodolite direction, and cracks in the coating layer occur. In this case, it not only maintains the integrity of the coating layer, but also protects the coating layer from cracking, and improves the mechanical properties such as overall tear resistance and strong dynamic load resistance of the coating layer. The addition of graphene hydroxide to the coating layer can broaden the glass transition temperature region of the coating layer, improve the damping performance of the coating layer, and significantly improve the tear resistance strength under high-speed impact load.

Advantageous effects of the present invention are as follows.

(1) the core of the explosion-proof and shock-proof material according to the present invention lies in the used explosion-proof and shock-proof coating layer; The explosion-proof and shock-proof coating layer greatly improves the negative Poisson's ratio effect of the preform in the matrix through the gradient spiral design and three-dimensional layered arrangement of the multi-stage auxiliary fibers of the preform; The explosion-proof and impact-proof performance of the coating layer of the same matrix composition in the direction of non-parallel load action can be improved to 298.5%.

(2) the multi-stage heterogeneous fiber preform of the coating layer of the present invention uses the warp and weft weave network of fiber bundles composed of multi-stage fibers with different elastic modulus to save cost as well as exhibit different advantages of fibers; By increasing the mechanical properties such as storage modulus of the fiber network through the design of the fiber gradient structure, and building the fiber dynamic interlocking mechanism through the warp and weft network nodes, the multi-stage heterogeneous fiber preform has a more pronounced negative Poisson's ratio effect. do.

(3) to solve the low-temperature brittleness of the coating layer by adding graphene hydroxide to the coating layer according to the present invention; In addition, the relatively large load-bearing performance of graphene hydroxide further improves the shear resistance and tear resistance of the coating layer, and effectively absorbs the load energy by causing the formation of a large amount of microcracks, thereby achieving the effect of protecting the internal structure. . Here, the tensile strength, elongation at break, and tear resistance strength of the composite coating layer of the explosion-proof and impact-proof multi-stage heterogeneous fiber preform can reach 47.3 MPa, 369%, and 187.4 MPa, respectively, and compared with the coating layer of the same matrix composition, the explosion-proof and anti-explosion-proof Impact performance is greatly improved.

1 is a schematic diagram of a three-stage heterogeneous fiber structure, where a is a core fiber, b1 is a single-stage auxiliary fiber, b2 is a two-stage auxiliary fiber, b3 is a three-stage auxiliary fiber, and θ is between the auxiliary fiber and the core fiber is the helix angle, D is the diameter of the core fiber, and d is the diameter of the auxiliary fiber.
2 is a schematic diagram of three-stage heterogeneous fiber action force deformation, where A1 is a front view of the three-stage heterogeneous fiber in the free initial state, A2 is a radial cross-sectional view of the three-stage heterogeneous fiber in the free initial state, and B1 is the three-stage heterogeneous fiber in the maximum stress state. It is a front view of the heterogeneous fiber, and B2 is a radial cross-sectional view of the three-stage heterogeneous fiber in the state of maximum stress.
3 is a schematic diagram of warp and weft plain weave structures of fibers in a multi-stage heterogeneous fiber preform, where x and y are distances between core fibers of the multi-stage heterogeneous fibers.

Hereinafter, the present invention will be further described in conjunction with Examples.

Example 1

The explosion-proof and shock-proof composite material includes a substrate and an explosion-proof and shock-proof coating layer covered on the substrate. The substrate is concrete. The explosion-proof and impact-proof coating layer is formed by curing a paint coated on a substrate, and the paint is an epoxy resin sufficiently dispersed by adding graphene hydroxide; The weight fraction of the graphene hydroxide in the paint is 0.4%. A two-stage heterogeneous fiber preform arranged in parallel in two layers is provided on the explosion-proof and impact-proof coating layer. The projection angle of the multistage heterogeneous fibers between the two tiers heterogeneous fiber preforms in each adjacent layer is 5 degrees. The included angle between the plane on which the two tier heterogeneous fiber preforms of each layer is located and the direction of the impact load resisted by the coating layer is 60 degrees to be. The layer spacing of the adjacent two-tier heterogeneous fiber preforms is 15 mm.

A two-stage heterogeneous fiber preform having a negative Poisson's ratio effect is formed by plain weave with warp and weft yarns by a plurality of two-stage heterogeneous fibers. wherein the two-stage heterogeneous fibers are wound around a core fiber by multi-stage auxiliary fibers; The core fiber is a low modulus fiber, and the two-stage auxiliary fiber is a high modulus fiber having a different elastic modulus. The distance between the core fibers of the adjacent two-stage heterogeneous fibers is 15 mm. the low modulus fiber is a polyester fiber; The polyester fiber is a fiber bundle with a diameter of 450 μm, the elongation at break is 18%, the modulus of elasticity is 13.5 GPa, the density is 1.38 g/cm ³ , and has excellent acid and alkali resistance.

the first-stage auxiliary fiber is an aramid fiber, the elastic modulus is 50 GPa, the diameter is 150 μm, and the helix angle is 8°; The second-stage auxiliary fiber is an aluminum silicate fiber, has an elastic modulus of 480 GPa, a diameter of 75 μm, and a helix angle of 20°.

In the manufacturing method of the explosion-proof and shock-proof composite material, the specific manufacturing method is as follows.

(1) Processing manufacturing step of single-stage heterogeneous fiber embryonic structure: According to the spiral angle of the single-stage structure, the high-modulus fiber, which is a first-stage auxiliary fiber, is wound around a low-modulus fiber, which is a core fiber, to form a single-stage heterogeneous fiber embryo structure get

(2) step of curing treatment of single-stage heterogeneous fiber embryo structure: a curing agent is added to the epoxy resin and stirred sufficiently, wherein a mass ratio of the curing agent and the epoxy resin is 1.0:0.8; Then, the single-stage heterogeneous fiber embryonic structure prepared in step (1) is immersed, heated to 60° C. to sufficiently immerse the single-stage heterogeneous fiber embryonic structure, and then the hardening system is taken out, and left to stand until hardened, the single-stage heterogeneous fiber get structure; the epoxy resin is a bisphenol A type epoxy resin; The curing agent is at least one of polyamide, polyester resin, and an aliphatic amine-based curing agent.

(3) Processing manufacturing step of two-stage heterogeneous fiber structure: using the heterogeneous fibers obtained in step (2) as a single-stage structure, and sequentially performing steps (1) and (2) according to the helix angle of the two-stage structure to obtain a two-stage heterogeneous fiber structure.

(4) weaving manufacturing step of two-stage heterogeneous fiber preform: after weaving the obtained two-stage heterogeneous fibers into warp and weft plain weave structure by warp and weft plain weave method along the warp and weft direction, warp and weft the curing system according to step (2) A two-stage heterogeneous fiber preform is obtained by sufficiently coating all warp yarns and weft yarn intersections of the weft yarn plain weave structure, and allowing it to stand until cured.

(5) manufacturing step of explosion-proof and impact-proof composite material: adding graphene hydroxide having a mass fraction of 0.4% to the paint, and sufficiently dispersing it by ultrasonic dispersion to obtain and stock up a modified paint; disposing one layer of heterogeneous fiber preform on the surface of the substrate, and pouring, coating, or spraying 20 mm of the modified paint onto the surface of the substrate to cure; Then, the above steps are repeated to obtain the explosion-proof and shock-proof composite material.

Example 2

The explosion-proof and shock-proof composite material includes a substrate and an explosion-proof and shock-proof coating layer covered on the substrate. The substrate is ceramic. The explosion-proof and impact-proof coating layer is formed by curing a paint coated on a substrate, and the paint is polyurea sufficiently dispersed by adding graphene hydroxide; The weight fraction of the graphene hydroxide in the paint is 0.5%. A two-stage heterogeneous fiber preform arranged in parallel in three layers is provided on the explosion-proof and impact-proof coating layer. The projected included angle of the multi-stage heterogeneous fibers between the three-stage heterogeneous fiber preforms in each adjacent layer is 15°. The included angle between the plane on which the three-layer heterogeneous fiber preform of each layer is located and the direction of the impact load resisted by the coating layer is 46°. The layer spacing of the adjacent three-tier heterogeneous fiber preform is 5 mm.

In the three-stage heterogeneous fiber preform having the negative Poisson's ratio effect, the distance between the core fibers of the adjacent three-stage heterogeneous fibers is 5 mm. the low modulus fiber is a polyethylene fiber; A fiber bundle with a diameter of 380 μm, an elastic modulus of 4 GPa, an elongation at break of 15%, and a density of 0.91 g/cm³.

the first stage auxiliary fiber is an aramid fiber, the elastic modulus is 85 GPa, the diameter is 243 μm, and the helix angle is 7°; the second stage auxiliary fiber is an ultra-high molecular weight polyethylene fiber, an elastic modulus of 130 GPa, a diameter of 149 μm, and a helix angle of 20°; The third-stage auxiliary fiber is a steel fiber and a carbon fiber, wherein the elastic modulus of the steel fiber is 205 GPa, the elastic modulus of the carbon fiber is 205 GPa, the diameter of both the steel fiber and the carbon fiber is 141 μm, and the carbon fiber and The helix angles of the steel fibers are all 35°.

In the manufacturing method of the explosion-proof and shock-proof composite material, the specific manufacturing method is as follows.

(1) Processing manufacturing step of single-stage heterogeneous fiber embryo structure: According to the spiral angle of the single-stage structure, the high-modulus fiber, which is a first-stage auxiliary fiber, is wound around a low-modulus fiber, which is a core fiber, to form a single-stage heterogeneous fiber embryo structure get

(2) curing treatment step of single-stage heterogeneous fiber embryo structure: a curing agent is added to the epoxy resin and stirred sufficiently, wherein the weight ratio of the curing agent to the epoxy resin is 1.0:1.1; Then, the single-stage heterogeneous fiber embryonic structure prepared in step (1) is immersed, heated to 80° C. to sufficiently immerse the single-stage heterogeneous fiber embryonic structure, and then the hardening system is taken out, and left to stand until hardened, the single-stage heterogeneous fiber get the structure the epoxy resin is a bisphenol A type epoxy resin; The curing agent is at least one of polyamide, polyester resin, and an aliphatic amine-based curing agent.

(3) Processing manufacturing step of three-stage heterogeneous fiber structure: using the heterogeneous fibers obtained in step (2) as a single-stage structure, and sequentially performing steps (1) and (2) according to the helix angle of the three-stage structure to obtain a three-stage heterogeneous fiber structure.

(4) weaving manufacturing step of three-tier heterogeneous fiber preform: after weaving the obtained three-tier heterogeneous fiber into warp and weft plain weave structure by warp and weft plain weave method along the warp and weft direction, warp and weft the curing system according to step (2) A three-tier heterogeneous fiber preform is obtained by sufficiently coating all warp yarns and weft yarn intersection points of the weft yarn plain weave structure, and allowing it to stand until cured.

(5) manufacturing step of explosion-proof and impact-proof composite material: adding graphene hydroxide having a mass fraction of 0.5% to the paint, and sufficiently dispersing it by ultrasonic dispersion to obtain and stock up a modified paint; disposing one layer of three-layer heterogeneous fiber preform on the surface of the substrate, and pouring, coating, or spraying 8 mm of the modified paint onto the surface of the substrate to cure; Then, the above steps are repeated to obtain the explosion-proof and shock-proof composite material.

Example 3

The explosion-proof and shock-proof composite material includes a substrate and an explosion-proof and shock-proof coating layer covered on the substrate. The substrate is low carbon steel. The explosion-proof and impact-proof coating layer is formed by curing a paint coated on a substrate, and the paint is a polyurethane sufficiently dispersed by adding graphene hydroxide; The weight fraction of the graphene hydroxide in the paint is 0.8%. A four-layer heterogeneous fiber preform arranged in parallel in four layers is provided on the explosion-proof and impact-proof coating layer. The projected included angle of the multi-stage heterogeneous fibers between the four-stage heterogeneous fiber preforms of each of the adjacent layers is 35°. The included angle between the plane on which the four-layer heterogeneous fiber preform of each layer is located and the direction of the impact load resisted by the coating layer is 90°. The layer spacing of the adjacent four tier heterogeneous fiber preforms is 4 mm.

In the four-stage heterogeneous fiber preform with negative Poisson's ratio effect, the distance between the core fibers of the adjacent four-stage heterogeneous fibers is 25 mm. the low modulus fiber is a polyphenylene sulfide fiber; With a fiber bundle with a diameter of 415 μm, the modulus of elasticity is 5.94 GPa, and the elongation at break is 30%.

the first-stage auxiliary fiber is a polyarylate fiber, an elastic modulus of 50 GPa, a diameter of 272 μm, and a helix angle of 6°; the second stage auxiliary fiber is a polybenzodioxazole fiber, the modulus of elasticity is 56 GPa, the diameter is 223 μm, and the helix angle is 11°; the third-stage auxiliary fiber is an ultra-high molecular weight polyethylene fiber, an elastic modulus of 65 GPa, a diameter of 145 μm, and a helix angle of 18°; The fourth-stage auxiliary fiber is an aluminum oxide fiber, has an elastic modulus of 455 GPa, a diameter of 125 μm, and a helix angle of 31°.

In the manufacturing method of the explosion-proof and shock-proof composite material, the specific manufacturing method is as follows.

(1) Processing manufacturing step of single-stage heterogeneous fiber embryonic structure: According to the spiral angle of the single-stage structure, the high-modulus fiber, which is a first-stage auxiliary fiber, is wound around a low-modulus fiber, which is a core fiber, to form a single-stage heterogeneous fiber embryo structure get

(2) curing treatment step of single-stage heterogeneous fiber embryo structure: a curing agent is added to the epoxy resin and stirred sufficiently, wherein the mass ratio of the curing agent to the epoxy resin is 1.0:1.0; Then, the single-stage heterogeneous fiber embryonic structure prepared in step (1) is immersed, heated to 50° C. to sufficiently immerse the single-stage heterogeneous fiber embryonic structure, and then the hardening system is taken out, and left to stand until hardened, the single-stage heterogeneous fiber get the structure the epoxy resin is a bisphenol A type epoxy resin; The curing agent is at least one of polyamide, polyester resin, and an aliphatic amine-based curing agent.

(3) Process manufacturing step of four-stage heterogeneous fiber structure: using the heterogeneous fibers obtained in step (2) as a one-stage structure, and sequentially performing steps (1) and (2) according to the helix angle of the four-stage structure to obtain a four-stage heterogeneous fiber structure.

(4) weaving manufacturing step of 4-layer heterogeneous fiber preform: After weaving the obtained 4-layer heterogeneous fibers into warp and weft plain weave structure by warp and weft plain weave method according to the warp and weft direction, warp and weft the curing system according to step (2) A four-layer heterogeneous fiber preform is obtained by sufficiently coating all warp yarns and weft yarn intersections of the weft yarn plain weave structure, and allowing it to stand until cured.

(5) manufacturing step of explosion-proof and impact-proof composite material: adding graphene hydroxide having a mass fraction of 0.8% to the paint, and sufficiently dispersing it by ultrasonic dispersion to obtain and stock up a modified paint; disposing one layer of four-layer heterogeneous fiber preform on the surface of the substrate, and pouring, coating, or spraying 5 mm of the modified paint onto the surface of the substrate to cure; Then, the above steps are repeated to obtain the explosion-proof and shock-proof composite material.

Example 4

The explosion-proof and shock-proof composite material includes a substrate and an explosion-proof and shock-proof coating layer covered on the substrate. The substrate is a ceramic substrate composite material. The explosion-proof and impact-proof coating layer is formed by curing a paint coated on a substrate, and the paint is a phenol resin sufficiently dispersed by adding graphene hydroxide; The weight fraction of the graphene hydroxide in the paint is 1.1%. A 5-stage heterogeneous fiber preform arranged in parallel in two layers is provided on the explosion-proof and impact-proof coating layer. The projected included angle of the multistage heterogeneous fibers between the five tiers heterogeneous fiber preforms of each adjacent layer is 46°. to be. The layer spacing of the adjacent 5 tier heterogeneous fiber preforms is 8 mm.

In the 5-stage heterogeneous fiber preform with negative Poisson's ratio effect, the distance between the core fibers of the adjacent 5-stage heterogeneous fibers is 30 mm. the low modulus fiber is a polyester fiber; The diameter of the polyester fiber is 670 μm, the density is 1.34 g/cm ³ , the modulus of elasticity is 13.55 GPa, the elongation at break is 20%, and it is a soft chain fiber.

the first-stage auxiliary fiber is an aramid fiber, the elastic modulus is 50 GPa, the diameter is 230 μm, and the helix angle is 7°; the auxiliary fiber of the second stage is a quartz fiber, the modulus of elasticity is 78 GPa, the diameter is 125 μm, the helix angle is 10°, the auxiliary fiber of the third stage is a polyarylate fiber, the modulus of elasticity is 87 GPa; , the diameter is 90 μm, the helix angle is 24°, the fourth stage auxiliary fiber is a basalt fiber, the elastic modulus is 111 GPa, the diameter is 77 μm, the helix angle is 35°; The fifth stage auxiliary fiber is an aluminum oxide fiber, has an elastic modulus of 459 GPa, a diameter of 71 μm, and a helix angle of 50°.

In the manufacturing method of the explosion-proof and shock-proof composite material, the specific manufacturing method is as follows.

(1) Processing manufacturing step of single-stage heterogeneous fiber embryonic structure: According to the spiral angle of the single-stage structure, the high-modulus fiber, which is a first-stage auxiliary fiber, is wound around a low-modulus fiber, which is a core fiber, to form a single-stage heterogeneous fiber embryo structure get

(2) curing treatment step of single-stage heterogeneous fiber embryo structure: a curing agent is added to the epoxy resin and stirred sufficiently, wherein the mass ratio of the curing agent to the epoxy resin is 1.0:1.2; Then, the single-stage heterogeneous fiber embryonic structure prepared in step (1) is immersed, heated to 70° C. to sufficiently immerse the single-stage heterogeneous fiber embryonic structure, and then the hardening system is taken out, and left to stand until hardened, the single-stage heterogeneous fiber get the structure the epoxy resin is a bisphenol A type epoxy resin; The curing agent is at least one of polyamide, polyester resin, and an aliphatic amine-based curing agent.

(3) Processing manufacturing step of five-stage heterogeneous fiber structure: using the heterogeneous fibers obtained in step (2) as a one-stage structure, and sequentially performing steps (1) and (2) according to the helix angle of the five-stage structure to obtain a five-stage heterogeneous fiber structure.

(4) weaving manufacturing step of 5-stage heterogeneous fiber preform: After weaving the obtained 5-stage heterogeneous fibers into warp and weft plain weave structure by warp and weft plain weave method along the warp and weft direction, warp and weft the curing system according to step (2) All warp and weft intersections of the weft yarn plain weave structure are sufficiently coated, and left to stand until cured to obtain a 5-stage heterogeneous fiber preform.

(5) manufacturing step of explosion-proof and impact-proof composite material: adding graphene hydroxide having a mass fraction of 1.1% to the paint, and sufficiently dispersing it by ultrasonic dispersion to obtain and stock up a modified paint; disposing one layer of five-layer heterogeneous fiber preform on the surface of the substrate, and pouring, coating, or spraying 10 mm of the modified paint onto the surface of the substrate to cure; Then, the above steps are repeated to obtain the explosion-proof and shock-proof composite material.

Example 5

The explosion-proof and shock-proof composite material includes a substrate and an explosion-proof and shock-proof coating layer covered on the substrate. The substrate is an ABS resin polymer material. The explosion-proof and impact-proof coating layer is formed by curing a paint coated on a substrate, and the paint is an organosilicon resin sufficiently dispersed by adding graphene hydroxide; The weight fraction of the graphene hydroxide in the paint is 1.6%. A six-layer heterogeneous fiber preform arranged in parallel in five layers is provided on the explosion-proof and impact-proof coating layer. The projected included angle of the multi-stage heterogeneous fibers between the six-stage heterogeneous fiber preforms in each adjacent layer is 67°. The included angle between the plane on which the six-layer heterogeneous fiber preform of each layer is located and the direction of the impact load resisted by the coating layer is 75°. The interlayer spacing of the adjacent six tier heterogeneous fiber preforms is 6 mm.

In the six-stage heterogeneous fiber preform having the negative Poisson's ratio effect, the distance between the core fibers of the adjacent six-stage heterogeneous fibers is 40 mm. the low modulus fiber is a polyvinyl alcohol fiber; Polyamide fibers are long fibers, with a diameter of 485 μm, an elongation at break of 24%, a modulus of elasticity of 5.23 GPa, and a density of 1.16 g/cm ³ .

the first stage auxiliary fiber is an aramid fiber, the modulus of elasticity is 72 GPa, the diameter is 285 μm, and the helix angle is 7°; the second-stage auxiliary fiber is a polyarylate fiber, an elastic modulus of 120 GPa, a diameter of 226 μm, and a helix angle of 15°; the third-stage auxiliary fiber is a steel fiber, the elastic modulus is 210 GPa, the diameter is 180 μm, and the helix angle is 25°; the fourth stage auxiliary fiber is silicon carbide fiber, the elastic modulus is 290 GPa, the diameter is 142 μm, and the helix angle is 34°; the fifth stage auxiliary fiber is an aluminum oxide fiber, the elastic modulus is 373 GPa, the diameter is 114 μm, and the helix angle is 40°; The sixth stage auxiliary fiber is an aluminum silicate fiber, has an elastic modulus of 481 GPa, a diameter of 100 μm, and a helix angle of 50°.

In the manufacturing method of the explosion-proof and shock-proof composite material, the specific manufacturing method is as follows.

(1) Processing manufacturing step of single-stage heterogeneous fiber embryonic structure: According to the spiral angle of the single-stage structure, the high-modulus fiber, which is a first-stage auxiliary fiber, is wound around a low-modulus fiber, which is a core fiber, to form a single-stage heterogeneous fiber embryo structure get

(2) step of curing treatment of single-stage heterogeneous fiber embryo structure: a curing agent is added to the epoxy resin and stirred sufficiently, wherein a mass ratio of the curing agent and the epoxy resin is 1.0:0.8; Then, the single-stage heterogeneous fiber embryonic structure prepared in step (1) is immersed, heated to 75°C to sufficiently immerse the single-stage heterogeneous fiber embryonic structure, and then the hardening system is taken out, and left to stand until hardened, the single-stage heterogeneous fiber get the structure the epoxy resin is a bisphenol A type epoxy resin; The curing agent is at least one of polyamide, polyester resin, and an aliphatic amine-based curing agent.

(3) Processing manufacturing step of 6-stage heterogeneous fiber structure: using the heterogeneous fibers obtained in step (2) as a 1-stage structure, and sequentially performing steps (1) and (2) according to the helix angle of the 6-stage structure to obtain a 6-stage heterogeneous fiber structure.

(4) weaving manufacturing step of 6-layer heterogeneous fiber preform: After weaving the obtained 6-layer heterogeneous fiber into warp and weft plain weave structure by warp and weft plain weave method along the warp and weft direction, warp and weft the curing system according to step (2) A six-layer heterogeneous fiber preform is obtained by sufficiently coating all warp yarns and weft yarn intersection points of the weft yarn plain weave structure, and allowing it to stand until cured.

(5) manufacturing step of explosion-proof and impact-proof composite material: add graphene hydroxide having a mass fraction of 1.6% to the paint, and sufficiently disperse it by ultrasonic dispersion to obtain and stock up a modified paint; disposing one layer of six-layer heterogeneous fiber preform on the surface of the substrate, and pouring, coating, or spraying 8 mm of the modified paint onto the surface of the substrate to cure; Then, the above steps are repeated to obtain the explosion-proof and shock-proof composite material.

Example 6

The explosion-proof and shock-proof composite material includes a substrate and an explosion-proof and shock-proof coating layer covered on the substrate. The substrate is glass. The explosion-proof and impact-proof coating layer is formed by curing a paint coated on a substrate, and the paint is a urea-formaldehyde resin sufficiently dispersed by adding graphene hydroxide; The weight fraction of the graphene hydroxide in the paint is 0.3%. A seven-layer heterogeneous fiber preform arranged in parallel in five layers is provided on the explosion-proof and impact-proof coating layer. The projection angle of the multistage heterogeneous fibers between the 7 tiers heterogeneous fiber preforms in each adjacent layer is 85°. to be. The layer spacing of the adjacent 7-tier heterogeneous fiber preforms is 2 mm.

In the 7-stage heterogeneous fiber preform with negative Poisson's ratio effect, the distance between the core fibers of the adjacent 7-stage heterogeneous fibers is 50 mm. the low modulus fiber is a polyimide fiber; Here, the modulus of elasticity is 12 GPa, the density is 2.35 g/cm ³ , the diameter is 600 μm, and the elongation at break is 29%.

the first-stage auxiliary fiber is alkali-resistant glass fiber, the elastic modulus is 74 GPa, the diameter is 305 μm, and the helix angle is 5°; the second stage auxiliary fiber is an ultra-high molecular weight polyethylene fiber, an elastic modulus of 100 GPa, a diameter of 200 μm, and a helix angle of 14°; the third-stage auxiliary fiber is silicon carbide fiber, the elastic modulus is 174 GPa, the diameter is 152 μm, and the helix angle is 24°; the fourth stage auxiliary fiber is a steel fiber, the elastic modulus is 202 GPa, the diameter is 124 μm, and the helix angle is 33°; the fifth stage auxiliary fiber is carbon fiber, the elastic modulus is 245 GPa, the diameter is 102 μm, and the helix angle is 40°; the sixth stage auxiliary fiber is an aluminum oxide fiber, the elastic modulus is 351 GPa, the diameter is 76 μm, and the helix angle is 50°; The seventh-stage auxiliary fiber is a silicon carbide fiber, has an elastic modulus of 462 GPa, a diameter of 41 μm, and a helix angle of 60°.

In the manufacturing method of the explosion-proof and shock-proof composite material, the specific manufacturing method is as follows.

(1) Processing manufacturing step of single-stage heterogeneous fiber embryonic structure: According to the spiral angle of the single-stage structure, the high-modulus fiber, which is a first-stage auxiliary fiber, is wound around a low-modulus fiber, which is a core fiber, to form a single-stage heterogeneous fiber embryo structure get

(2) step of curing treatment of single-stage heterogeneous fiber embryo structure: a curing agent is added to the epoxy resin and stirred sufficiently, wherein a mass ratio of the curing agent to the epoxy resin is 1.0:0.9; Then, the single-stage heterogeneous fiber embryonic structure prepared in step (1) is immersed, heated to 65° C. to sufficiently immerse the single-stage heterogeneous fiber embryonic structure, and then the hardening system is taken out, and left to stand until hardened, the single-stage heterogeneous fiber get the structure the epoxy resin is a bisphenol A type epoxy resin; The curing agent is at least one of polyamide, polyester resin, and an aliphatic amine-based curing agent.

(3) Processing manufacturing step of seven-stage heterogeneous fiber structure: using the heterogeneous fibers obtained in step (2) as a one-stage structure, and sequentially performing steps (1) and (2) according to the helix angle of the seven-stage structure to obtain a 7-stage heterogeneous fiber structure.

(4) Weave manufacturing step of 7-tier heterogeneous fiber preform: After weaving the obtained 7-tier heterogeneous fiber into warp and weft plain weave structure by warp and weft plain weave method along the warp and weft direction, warp and weft the curing system according to step (2) A 7-layer heterogeneous fiber preform is obtained by sufficiently coating all warp yarns and weft yarn intersection points of the weft yarn plain weave structure, and allowing it to stand until cured.

(5) manufacturing step of explosion-proof and impact-proof composite material: add graphene hydroxide having a mass fraction of 0.3% to the paint, and sufficiently disperse it by ultrasonic dispersion to obtain and stock up a modified paint; disposing one layer of 7-layer heterogeneous fiber preform on the surface of the substrate, and pouring, coating, or spraying 4 mm of the modified paint onto the surface of the substrate to cure; Then, the above steps are repeated to obtain the explosion-proof and shock-proof composite material.

Control Example 1

Laying aramid fibers after general treatment on the surface of low carbon steel; The paint is an epoxy resin sufficiently dispersed by adding graphene hydroxide; The weight fraction of the graphene hydroxide in the paint is 0.4% (same as Example 1). The specific method is as follows. The two components are mixed and then sprayed on the surface of the substrate to form a coating layer with a thickness of 6 mm, then covered with one layer of aramid fiber, and sprayed with one layer of paint, the thickness of which is 6 mm and sequentially overlapping three times to form an explosion-proof and anti-ballistic coating layer, and the total thickness of the coating layer reaches 18 mm. By spraying on the surface of the low-carbon steel without a fiber mesh layer, an explosion-proof and anti-ballistic coating layer of the same thickness is formed, and its impact strength is used as a test standard.

A corresponding mechanical property test was performed on each of the composite coating layer samples prepared in Control Example 1 and Examples 1 to 6.

Fiber mechanical properties test: universal mechanical testing machine is used, the tensile speed is 5 mm/min, and the fiber length is 250 mm.

Poisson's ratio test: The digital speckle correlation method is used with the testing and calculation of universal mechanical testing machine, the load speed of mechanical testing machine is 5 mm/min.

Testing the mechanical properties of the composite coating layer: The tensile strength, elongation at break, tear resistance strength and impact strength of the material are obtained by testing with a universal testing machine according to ASTMD638, ASTM D638, and ASTM D624, respectively.

Table 1 Parameters of the fiber network of Control Example 1 and the fiber preforms prepared in Examples 1 to 6

Table 2 Mechanical properties test parameters of the explosion-proof and impact-proof composite coating layers prepared in Control Example 1 and Examples 1 to 6

As can be seen from Table 1, the Poisson's ratio of the fiber preforms prepared in Examples 1 to 6 was -5.77 to -10.64, and the Poisson's ratio of the fiber network according to the control example was 0.3. As can be seen from this, the Poisson's ratio effect of the multi-stage fiber preform according to the present invention is more significant compared to the fiber network of the prior art; As the stage number of auxiliary fibers in the fiber preform increases, the negative Poisson's ratio effect also gradually increases.

As can be seen from Table 2, the tensile strength of the composite coating layer prepared in Examples 1 to 6 is 36.4 to 47.3 MPa, the elongation at break is 343.6% to 369.0%, and the tear resistance strength is 149.6 kN/m to 187.4 kN/ m; Compared with Control Example 1, all were significantly improved, and in particular, the tear resistance strength was improved to 83.7%, indicating that the mechanical properties were greatly improved. In addition, compared with the same coating layer of the structure without fiber reinforcement, the impact resistance performance of the composite coating layer prepared in the present invention is amplified by 298.5%; This indicates that the gradient spiral design and three-dimensional layered arrangement of multi-stage auxiliary fibers in the preform of the composite coating layer have a remarkable effect in improving the shock and explosion-proof performance.

Claims (10)

An explosion-proof and impact-proof multi-stage heterogeneous fiber preform composite material comprising a substrate and an explosion-proof and impact-proof coating layer covered on the substrate,
The explosion-proof and shock-proof coating layer is formed by curing a paint coated on a substrate, and the paint is an alkyd resin, an acrylic resin, an epoxy resin, which is sufficiently dispersed by adding graphene hydroxide. , at least one of phenolic resin, urea-formaldehyde resin, organicsilicone resin, polyurethane, and polyurea; The weight fraction of the graphene hydroxide in the paint is 0.2% to 2.0%;
The explosion-proof and impact-proof coating layer is provided with a multi-stage heterogeneous fiber preform arranged in parallel in several layers; the fiber preform is formed by plain weave with warp and weft yarns by a plurality of multi-stage heterogeneous fibers; the multi-stage heterogeneous fibers are formed by winding a core fiber with a multi-stage auxiliary fiber; the core fiber is a low modulus fiber, and the multi-stage auxiliary fiber includes a high modulus fiber sequentially wound around the core fiber and having a higher modulus of elasticity than the core fiber; the modulus of elasticity of the one-stage auxiliary fiber in the multi-stage auxiliary fiber is 50 GPa to 90 GPa; The elastic modulus ratio of the N-th stage auxiliary fiber and the N-1 stage auxiliary fiber is 1.1 to 9.6, and N = 2 to 7; The diameter ratio of the core fiber to the first stage auxiliary fiber is 1.5 to 3.0, the diameter ratio of the core fiber to the Nth stage auxiliary fiber is 2.5 to 15.0, and the diameter ratio of the N stage auxiliary fiber to the N-1 stage auxiliary fiber is is 0.5 to 0.9, N is 2 to 7; The helix angle of the first stage auxiliary fiber is 2 ° to 8 °, the helix angle of the N-th stage auxiliary fiber is increased by 3 ° to 15 ° compared to the N-1 stage auxiliary fiber, and the helix of the N-th stage auxiliary fiber is The angle is 5 ° to 60 °, N is 2 to 7 explosion-proof and impact-proof multi-stage heterogeneous fiber preform composite material, characterized in that. According to claim 1,
the distance between the core fibers of the adjacent multi-stage heterogeneous fibers is between 2 mm and 50 mm; the modulus of elasticity of the low modulus fiber is 50 MPa to 50 GPa; the modulus of elasticity of the high modulus fiber is ≧50 GPa; The elastic modulus ratio of the N-th stage auxiliary fiber to the N-1 stage auxiliary fiber is 1.1 to 7.5, and N is 2 to 7; The diameter ratio of the core fiber to the first stage auxiliary fiber is 1.5 to 2.5, the diameter ratio of the core fiber to the Nth stage auxiliary fiber is 2.5 to 10.0, and the helix angle of the Nth stage auxiliary fiber is 10 ° to 60 °, N is 2 to 7 explosion-proof and impact-proof multi-stage heterogeneous fiber preform composite material, characterized in that. 3. The method of claim 2,
An explosion-proof and impact-proof multi-stage heterogeneous fiber preform composite material, characterized in that the projected narrow angle of the multi-stage heterogeneous fibers between the multi-stage heterogeneous fiber preforms in each adjacent layer is 5° to 90°. 3. The method of claim 2,
Explosion-proof and impact-proof multi-stage heterogeneous fiber preform composite material, characterized in that the included angle between the plane on which the multi-stage heterogeneous fiber preform of each layer is located and the direction of the impact load resisted by the coating layer is 5° to 90°. 4. The method of claim 3,
The explosion-proof and impact-proof multi-stage heterogeneous fiber preform composite material, characterized in that the layer spacing of the adjacent multi-stage heterogeneous fiber preform is 2 mm to 20 mm. 6. The method of claim 5,
The low modulus fiber is polyethylene fiber, polyvinyl alcohol fiber, polyvinyl formal fiber, polyvinyl chloride fiber, polypropylene fiber. , polyacrylonitrile fiber, polyamide fiber, polyimide fiber, polyester fiber, polyurethane fiber, cellulose fiber, at least one of polytetrafluoroethylene fiber and polyphenylene sulfide fiber; The high modulus fiber is an aramid fiber, polybenzimidazole fiber, polybenzodioxazole fiber, polyarylate fiber, ultra-high molecular weight polyethylene fiber, glass fiber ( glass fiber, carbon fiber, steel fiber, continuous basalt fiber, silicon carbide fiber, magnesium oxide fiber, aluminum oxide fiber (alu) Minium oxide fiber), silica fiber (silica fiber), quartz fiber (quartz fiber), aluminum silicate fiber (alu minium silicate fiber), graphene fiber (graphene fiber) and boron fiber (boron fiber) characterized in that at least one Explosion-proof and shock-proof multi-stage heterogeneous fiber preform composite material. 6. The method of claim 5,
The base material is an explosion-proof and impact-proof multi-stage heterogeneous fiber preform composite material, characterized in that at least one of metal, ceramic, glass, concrete, polymer and composite material. A method for producing an explosion-proof and impact-proof multi-stage heterogeneous fiber preform composite material according to any one of claims 1 to 7, comprising:
The specific manufacturing method is,
(1) According to the helix angle of the single-stage structure, winding the high-modulus fiber, which is a first-stage auxiliary fiber, on a low-modulus fiber, which is a core fiber, to obtain a single-stage heterogeneous fiber embryonic structure, processing manufacturing step of a single-stage heterogeneous fiber embryo structure ;
(2) adding a curing agent to the epoxy resin and sufficiently stirring, wherein the mass ratio of the curing agent to the epoxy resin is 1.0:0.8 to 1.0:1.2; Then, the single-stage heterogeneous fiber embryonic structure prepared in step (1) is immersed, heated to 50° C. to 80° C. to sufficiently immerse the single-stage heterogeneous fiber embryonic structure, and then the hardening system is taken out, and left to stand until hardened. Hardening treatment step of the single-stage heterogeneous fiber embryonic structure to obtain a single heterogeneous fiber structure;
(3) using the heterogeneous fiber obtained in step (2) as a single-stage structure, and sequentially overlapping steps (1) and (2) according to the helix angle of the N-stage structure to obtain an N-stage heterogeneous fiber structure, , N is 2 to 7, processing manufacturing step of the multi-stage heterogeneous fiber structure;
(4) After weaving the obtained N-stage heterogeneous fibers into warp and weft plain weave structures by warp and weft plain weave along the warp and weft directions, the curing system according to step (2) is applied to all warp and weft intersections of warp and weft plain weave structures. A step of weaving manufacturing of a multi-stage heterogeneous fiber preform, in which N is 2 to 7, by sufficiently coating and allowing to stand until cured to obtain an N-stage heterogeneous fiber preform; and
(5) adding graphene hydroxide having a mass fraction of 0.2% to 2.0% to the paint, and sufficiently dispersing it by ultrasonic dispersion to obtain and stockpile a modified paint; disposing one layer of multi-stage heterogeneous fiber preform on the surface of the substrate, and pouring, coating, or spraying the modified paint of 2 mm to 20 mm on the surface of the substrate to cure; and then repeating the steps to obtain the explosion-proof and impact-proof composite material, comprising the step of manufacturing an explosion-proof and impact-proof composite material. 9. The method of claim 8,
The epoxy resin according to step (2) is a bisphenol A epoxy resin; The curing agent is polyamide (polyamide), polyester resin (polyester resin), aliphatic amine (aliphatic a mine) method of manufacturing an explosion-proof and impact-proof multi-stage heterogeneous fiber preform composite material, characterized in that at least one of the curing agent. delete

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