CN114434917A - Penetration-resistant material and preparation method and application thereof - Google Patents

Penetration-resistant material and preparation method and application thereof Download PDF

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Publication number
CN114434917A
CN114434917A CN202210056183.3A CN202210056183A CN114434917A CN 114434917 A CN114434917 A CN 114434917A CN 202210056183 A CN202210056183 A CN 202210056183A CN 114434917 A CN114434917 A CN 114434917A
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layer
penetration
composite material
energy
graphene
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CN114434917B (en
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胡梦龙
杨海洋
甘顺昌
胡小刚
郑永
谷元
许双喜
张亚新
谭平华
彭超义
向中华
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Zhuzhou Times New Material Technology Co Ltd
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Zhuzhou Times New Material Technology Co Ltd
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Abstract

A penetration-proof material and a preparation method and application thereof are disclosed, wherein the penetration-proof material comprises the following components from outside to inside: the energy-absorbing and energy-absorbing composite material comprises an upper coating (1), a constraint layer (2), a ceramic layer (3), a support layer (4), an energy-dissipating layer (5), an energy-absorbing layer (7) and a lower coating (8), wherein the energy-dissipating layer (5) comprises a composite material A and a composite material B, the composite material A is a high-performance fiber-shear thickening fluid composite material, and the composite material B comprises at least one of a high-performance fiber-graphene and a high-performance fiber-graphene derivative composite material. The penetration-proof material is a composite material armor designed by comprehensively considering factors such as protectiveness, maneuverability and the like, can effectively reduce the surface density and thickness of a protection structure, and limits penetration damage to a small range.

Description

Penetration-resistant material and preparation method and application thereof
Technical Field
The invention belongs to the field of protective armor, and particularly relates to a penetration-resistant material, and a preparation method and application thereof.
Background
With the continuous improvement of the penetration capability of modern weapons, higher requirements are put on the protection performance of helicopter armors and tank armors, and the weight of bulletproof armors is heavier and heavier. However, the contradiction between the weight of the armor and its protection becomes the first problem to be solved in order to ensure the maneuverability of the combat equipment.
The metal bulletproof armor needs to continuously improve the thickness of bulletproof steel to achieve the effect of effective penetration of protective bullets, and the maneuverability of combat equipment can be greatly sacrificed. Therefore, researchers have developed bulletproof armors made of non-metallic materials. Non-metallic ceramic materials have been widely used in recent years as a replacement for metal materials for ballistic armor because of their low density, high modulus, high stiffness, and lack of hardness at high temperatures. However, ceramic materials have limitations in their application to ballistic armor, and the penetration action of a bullet tends to cause it to break down in its entirety, failing to resist successive penetration of the bullet. The kinetic energy of the existing armor cannot be completely absorbed when the existing armor resists penetration of the projectile, and partial impact is still transmitted to the combat equipment, so that impact is caused, and the running stability of the combat equipment is influenced. Therefore, the development trend of preparing the modern bulletproof armor is to select various materials for compounding.
Currently, many aspects of the preparation of bulletproof armor are in urgent need of improvement, which mainly show the following aspects: (1) the light weight of the armor is restricted by the protection requirement; (2) the armor has insufficient capability of resisting continuous penetration destruction; (3) the higher requirements of modern war on the protection performance of the armor cannot be met; (4) the damping energy absorption performance of the armor is still to be improved in order to ensure the stable operation of the combat equipment.
In order to solve the problems, systematic research and development on materials and overall structures of the bulletproof armor are needed.
Disclosure of Invention
The invention overcomes the defects and shortcomings in the background technology and provides an anti-penetration material and a preparation method and application thereof. In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a penetration-resistant material comprising, from the outside to the inside: the energy dissipation layer comprises a composite material A and a composite material B, the composite material A is a high-performance fiber-shear thickening fluid composite material, and the composite material B comprises at least one of a high-performance fiber-graphene and a high-performance fiber-graphene derivative composite material; more preferably, the composite material comprises a high-performance fiber-graphene oxide composite material.
The energy dissipation layer comprises a high-performance fiber-shear thickening liquid composite woven fabric composite material A and a high-performance fiber-graphene/graphene derivative composite woven fabric composite material B, wherein the high-performance fiber-shear thickening liquid composite woven fabric composite material is soft and hard under the impact of bullets, can absorb more impact energy, and meanwhile, the impact force dispersion area is increased;
the graphene and the derivatives thereof are used as a two-dimensional material, have good mechanical properties in a plane, are beneficial to transmitting stress waves generated by penetration of the projectile along the plane direction, enable impact energy to be dispersed uniformly in the plane of the armor, and improve the protective performance. In addition, the existence of graphene in the high-performance fiber-graphene composite woven fabric composite material and the high-performance fiber-graphene derivative composite material has a synergistic effect with the in-plane transmission of the fiber, so that the transmission of bullet shock wave energy is facilitated, on one hand, the energy transmission between the fiber and the fiber can be improved, on the other hand, the two-dimensional plane of the graphene in the thickness direction deflects under the penetration effect of the bullets, and the energy transmission between layers of woven fabrics in the thickness direction can be improved.
Preferably, the high-performance fiber comprises at least one selected from aramid II, aramid III or ultra-high molecular weight polyethylene; the shear thickening fluid is SiO2-a polyethylene glycol system.
Preferably, the composite material a and the composite material B are cross-laminated.
Preferably, a rubber layer is further arranged between the energy dissipation layer and the energy absorption layer.
The rubber layer can effectively dissipate the impact energy of the bullet and has the functions of buffering, shock absorption and damping energy absorption.
The rubber layer is arranged between the energy dissipation layer and the energy absorption layer, and the damping energy absorption and the buffering shock absorption are realized; secondly, the rigidity and the modulus of the rubber layer are small, so that the ballistic deflection of the projectile is easy to occur when the projectile penetrates the rubber layer, and the protective performance is enhanced.
Preferably, the rubber layer is provided with a cord fabric as a supporting framework, and the rubber comprises at least one of natural rubber, butyl rubber or chloroprene rubber.
Preferably, the ceramic layer is a ceramic splice plate formed by splicing a whole ceramic plate or regular polygonal ceramic plates and is made of Al2O3、SiC、B4C. BN or Si3N4At least one of; the supporting layer comprises carbon fibers; the restraint layer and the energy absorption layer comprise high-performance fibers; the upper and lower coatings include a polyurea coating. The polyurea coating has the characteristics of wear resistance and high hardness, and can effectively resist penetration of bullets.
Under the same technical concept, the invention also provides a preparation method of the penetration-resistant material, which comprises the following steps:
(1) preparing an energy dissipation layer: dipping and drying the high-performance fiber (I) by using a shear thickening solution to obtain a composite material A, dipping and treating the high-performance fiber (II) by using a prepreg adhesive solution containing graphene and/or graphene derivatives to obtain a composite material B, coating the prepreg adhesive on the surfaces of the composite material A and the composite material B, and performing hot-press bonding after cross lamination to obtain an energy dissipation layer;
(2) sequentially bonding the restraint layer, the ceramic layer, the support layer, the energy dissipation layer, the rubber layer and the energy absorption layer, and performing hot press molding to obtain an anti-penetration material main body;
(3) and polishing the main body of the penetration-proof material, and spraying the upper coating and the lower coating to obtain the penetration-proof material.
Preferably, the preparation method of the prepreg adhesive solution containing graphene and/or graphene derivatives in the step (1) comprises the following steps: adding graphene and/or a graphene derivative into a pre-impregnated adhesive solution, stirring and dispersing, and performing ultrasonic oscillation to obtain the pre-impregnated adhesive solution containing the graphene and/or the graphene derivative, wherein the pre-impregnated adhesive is prepared from the graphene and/or the graphene derivative in a mass ratio of 95: 5-97.5: 2.5; the pre-dipping adhesive solution containing the graphene and/or the graphene derivative accounts for 30-50% of the total weight of the composite material B.
Preferably, the shear thickening fluid is prepared by mixing SiO2The shear thickening liquid system of polyethylene glycol is diluted by adding ethanol, and the volume ratio of the ethanol to the shear thickening liquid is (1-3): 1.
Preferably, the hot pressing temperature in the step (1) is 110-130 ℃, and the pressure is 10-15 MPa.
Preferably, the adhesives in step (1) are all selected from the same kind, the support layer in step (2) is obtained by hot-press bonding of carbon fiber prepreg resin, the energy absorption layer is obtained by hot-press bonding of high-performance fiber prepreg resin, and the prepreg adhesives and the prepreg resin include at least one of epoxy resin, phenolic resin and polyurethane.
The same adhesive is selected to ensure that the two high-performance fiber composite materials have better interfacial cohesiveness and are not easy to generate interfacial debonding.
Preferably, the bonding in step (2) is performed by using an adhesive, wherein the rubber layer is bonded with the adjacent energy dissipation layer and the energy absorption layer by using a double-coating adhesive, and the adhesive comprises at least one of epoxy resin, phenolic resin, polyurethane, polyvinyl acetate, ethylene-vinyl acetate copolymer and polyvinyl acetal.
The energy absorption layer can absorb the residual energy of the bullet and ensure the protection performance of the armor.
Preferably, the hot pressing temperature in the step (2) is controlled to be 110-120 ℃, and the pressure is controlled to be 2-2.5 MPa; and (4) spraying the upper coating and the lower coating in the step (3) by spraying polyurea coatings on the upper surface and the lower surface of the armor main body.
Under the same technical concept, the invention also provides application of the penetration-proof material, and the penetration-proof material is applied to bulletproof equipment.
Compared with the prior art, the invention has the beneficial effects that:
(1) the penetration-proof material is a composite material armor designed by comprehensively considering factors such as protectiveness, maneuverability and the like, can effectively reduce the surface density and thickness of a protection structure, and limits penetration damage to a small range.
(2) The energy dissipation layer is obtained by alternately laminating and hot-pressing the high-performance fibers and the composite material of the shear thickening liquid, the graphene and the graphene derivative, and has higher energy transfer efficiency and can absorb and dissipate more energy compared with the energy dissipation layer obtained by hot-pressing and bonding only one high-performance fiber.
(3) According to the invention, the rubber layer is introduced into the penetration-resistant material laminated structure, and the cord fabric is arranged in the penetration-resistant material laminated structure to serve as a supporting framework, so that the damping energy absorption performance of the whole armor is improved, the impact generated by the kinetic energy release of the projectile can be better absorbed, and the operation stability of the combat equipment is ensured.
(4) The restraint layer is mainly used for preventing the ceramic layer from being integrally cracked and broken pieces from flying out, and the continuous penetration and destruction resisting capability of the armor is improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a schematic cross-sectional view of a penetration-preventing material of example 1;
in the figure: 1. coating; 2. a constraining layer; 3. a ceramic layer; 4. a support layer; 5. an energy dissipation layer; 6. a rubber layer; 7. an energy absorbing layer; 8. and (4) lower coating.
Detailed Description
In order to facilitate understanding of the invention, the invention will be described more fully and in detail with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1: a
A preparation method of penetration-resistant material comprises the following steps:
(1) the supporting layer is obtained by pre-impregnating a plurality of layers of carbon fiber woven fabrics with resin and then bonding the carbon fiber woven fabrics together through hot pressing, the pre-impregnated resin is epoxy resin, the mass ratio of the epoxy resin to the supporting layer is 30-40%, and the supporting layer with the thickness of 5mm is obtained by keeping the temperature and the pressure for 30min at the temperature of 120-150 ℃ and under the pressure of 15-20 MPa.
(2) In SiO2Adding ethanol into an STF system of a polyethylene glycol system for dilution, wherein the volume ratio of ethanol to STF is 3:1, putting the aramid fiber II woven fabric into the solution for dipping treatment, taking out, and drying for 8 hours at the temperature of 60-100 ℃ to obtain the aramid fiber II/STF composite woven fabric.
Adding graphene into epoxy resin, stirring and dispersing uniformly, then carrying out ultrasonic oscillation for 30min, and obtaining epoxy resin dispersion liquid containing graphene after uniform dispersion, wherein the mass ratio of the epoxy resin to the graphene is 95: 5; and (3) soaking the aramid fiber III woven fabric in an epoxy resin dispersion liquid containing graphene to obtain the aramid fiber III/graphene composite woven fabric, wherein the epoxy resin dispersion liquid containing the aramid fiber III is 40-50% of the total weight of the fiber prepreg cloth.
Coating epoxy resin adhesive on the surfaces of aramid fiber II/STF composite woven fabric and aramid fiber III/graphene composite woven fabric, stacking the aramid fiber II/STF composite woven fabric and the aramid fiber III/graphene composite woven fabric in a multilayer manner, and keeping the temperature and pressure for 20min under the conditions of 110-130 ℃ and 10-15 MPa to obtain an energy dissipation layer with the thickness of 5 mm.
(3) The energy absorption layer is obtained by pre-impregnating resin on a plurality of layers of ultra-high molecular weight polyethylene fiber woven fabric and then bonding the layers together through hot pressing, wherein the pre-impregnated resin is epoxy resin, the mass ratio of the epoxy resin to the second fiber composite layer is 25-30%, and the heat preservation and pressure maintaining are carried out for 30min under the conditions of 120-150 ℃ and 18-25 MPa to obtain the energy absorption layer with the thickness of 5 mm.
(4) Sequentially stacking a restraint layer, a ceramic layer, a supporting layer, an energy dissipation layer, a rubber layer and an energy absorption layer, wherein the restraint layer is made of ultra-high molecular weight polyethylene UD cloth, the ceramic layer is a B4C ceramic whole plate with the thickness of 10mm, the rubber layer is a chloroprene rubber layer with the thickness of 5mm, and the interior of the rubber layer is provided with cord cloth as a reinforcing framework; bonding the rubber layer with the adjacent energy dissipation layer and energy absorption layer by using a double-coating adhesive, bonding the interfaces of the rest layers by using epoxy resin, standing for 12 hours at room temperature, and then performing hot-press compounding in an autoclave, wherein the hot-press technological conditions are as follows: controlling the temperature at 110-120 ℃, controlling the pressure at 2-2.5 MPa, preserving heat and pressure for 1h to obtain the armor main body, polishing and flattening the surface of the armor main body by using a grinding wheel, and then respectively spraying polyurea coatings with the thickness of 0.5mm on the upper surface and the lower surface of the armor main body.
A penetration-resistant material comprising, from the outside to the inside: the energy-absorbing coating comprises an upper coating 1, a constraint layer 2, a ceramic layer 3, a supporting layer 4, an energy-absorbing layer 5, an energy-absorbing layer 7 and a lower coating 8, wherein the energy-absorbing layer 5 comprises aramid fiber II/STF composite woven fabric and aramid fiber III/graphene composite woven fabric.
The penetration-resistant material of the embodiment is applied to bulletproof armor.
FIG. 1 is a schematic cross-sectional view of a penetration-preventing material of example 1; as can be seen from the figure, the upper coating 1, the constraint layer 2, the ceramic layer 3, the support layer 4, the energy dissipation layer 5, the energy absorption layer 7 and the lower coating 8 are sequentially arranged and compounded to form the penetration-resistant material.
Example 2:
example 2 differs from example 1 in that SiO2The volume ratio of STF system to ethanol dilution of polyethylene glycol system is 1: 1.
Example 3:
the difference between the embodiment 3 and the embodiment 1 is that graphene oxide is used as graphene.
The test shows that SiO2The puncture resistance effect of the STF system of the polyethylene glycol system and ethanol with the dilution volume ratio of 1:1 is better than 3: 1; due to the polar groups on the surface of the graphene oxide, the graphene oxide is well combined with a fiber interface, and the mechanical property of the graphene oxide is superior to that of the graphene.

Claims (14)

1. A penetration-preventing material is characterized by comprising from outside to inside: the energy-absorbing and energy-absorbing composite material comprises an upper coating (1), a constraint layer (2), a ceramic layer (3), a support layer (4), an energy-dissipating layer (5), an energy-absorbing layer (7) and a lower coating (8), wherein the energy-dissipating layer (5) comprises a composite material A and a composite material B, the composite material A is a high-performance fiber-shear thickening fluid composite material, and the composite material B comprises at least one of a high-performance fiber-graphene and a high-performance fiber-graphene derivative composite material.
2. The penetration-resistant material of claim 1 wherein the high-performance fibers comprise at least one selected from aramid ii, aramid iii, or ultra-high molecular weight polyethylene; the shear thickening fluid is SiO2-a polyethylene glycol system.
3. The penetration-resistant material of claim 1 or 2, wherein the composite material a and the composite material B are cross-laminated.
4. The penetration-resistant material of claim 1, wherein a rubber layer (6) is further provided between the energy-dissipating layer (5) and the energy-absorbing layer (7).
5. The penetration-resistant material of claim 4 wherein the rubber layer (6) has a scrim as a supporting skeleton, the rubber comprising at least one of natural rubber, butyl rubber or neoprene.
6. The penetration-resistant material of any one of claims 1-5 wherein the ceramic is a ceramicThe layer (3) is a ceramic splice plate made of Al and formed by splicing a ceramic whole plate or regular polygonal ceramic plates2O3、SiC、B4C. BN or Si3N4At least one of; the supporting layer (4) comprises carbon fibers; the restraint layer (2) and the energy absorption layer (7) comprise high-performance fibers; the upper coating (1) and the lower coating (2) comprise polyurea coatings.
7. A method for preparing penetration-resistant material according to any one of claims 1 to 6, comprising the steps of:
(1) preparing an energy dissipation layer: dipping and drying the high-performance fiber (I) by using a shear thickening solution to obtain a composite material A, dipping and treating the high-performance fiber (II) by using a prepreg adhesive solution containing graphene and/or graphene derivatives to obtain a composite material B, coating the prepreg adhesive on the surfaces of the composite material A and the composite material B, and performing hot-press bonding after cross lamination to obtain an energy dissipation layer;
(2) sequentially bonding the restraint layer, the ceramic layer, the support layer, the energy dissipation layer, the rubber layer and the energy absorption layer, and performing hot press molding to obtain an anti-penetration material main body;
(3) and (5) polishing the penetration-proof material main body, and spraying the upper coating and the lower coating to obtain the penetration-proof material.
8. The method for preparing penetration-resistant material according to claim 7, wherein the prepreg adhesive solution containing graphene and/or graphene derivatives in the step (1) is prepared by: adding graphene and/or a graphene derivative into a pre-impregnated adhesive solution, stirring and dispersing, and performing ultrasonic oscillation to obtain the pre-impregnated adhesive solution containing the graphene and/or the graphene derivative, wherein the pre-impregnated adhesive is prepared from the graphene and/or the graphene derivative in a mass ratio of 95: 5-97.5: 2.5; the pre-dipping adhesive solution containing the graphene and/or the graphene derivative accounts for 30-50% of the total weight of the composite material B.
9. The method of making an anti-penetration material of claim 7, wherein the shear thickening fluid is introduced into the fluidPer in SiO2The shear thickening liquid system of polyethylene glycol is diluted by adding ethanol, and the volume ratio of the ethanol to the shear thickening liquid is (1-3): 1.
10. The method for preparing penetration preventing material according to claim 7 or 8, wherein the hot pressing temperature in step (1) is 110 to 130 ℃, and the pressure is 10 to 15 MPa.
11. The method for preparing the penetration-preventing material according to claim 7 or 8, wherein the prepreg adhesives in the step (1) are all selected from the same kind, the supporting layer in the step (2) is obtained by hot-press bonding of carbon fiber prepreg resin, the energy-absorbing layer is obtained by hot-press bonding of high-performance fiber prepreg resin, and the prepreg adhesives and the prepreg resin comprise at least one of epoxy resin, phenolic resin and polyurethane.
12. The method for preparing penetration-resistant material according to claim 7, wherein the bonding in step (2) is performed by using an adhesive, wherein the rubber layer and the adjacent energy-dissipating layer and energy-absorbing layer are bonded by using a double-coating adhesive, and the adhesive comprises at least one of epoxy resin, phenolic resin, polyurethane, polyvinyl acetate, ethylene-vinyl acetate copolymer and polyvinyl acetal.
13. The method for preparing penetration-preventing material according to claim 7, wherein the hot pressing temperature in step (2) is controlled to 110 to 120 ℃, and the pressure is controlled to 2 to 2.5 MPa; and (4) spraying the upper coating and the lower coating in the step (3) by spraying polyurea coatings on the upper surface and the lower surface of the armor main body.
14. Use of penetration-resistant material according to any of claims 1-6 in ballistic-resistant equipment.
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CN114750487A (en) * 2022-05-25 2022-07-15 江南大学 Radiation-proof multi-gradient anti-explosion composite material and preparation method thereof

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CN205482596U (en) * 2016-01-05 2016-08-17 武汉理工大学 Novel composite armor
CN111805983A (en) * 2020-07-09 2020-10-23 浙江立泰复合材料股份有限公司 Bulletproof unit and manufacturing process thereof

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* Cited by examiner, † Cited by third party
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CN114750487A (en) * 2022-05-25 2022-07-15 江南大学 Radiation-proof multi-gradient anti-explosion composite material and preparation method thereof

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