CN114434917B - 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
CN114434917B
CN114434917B CN202210056183.3A CN202210056183A CN114434917B CN 114434917 B CN114434917 B CN 114434917B CN 202210056183 A CN202210056183 A CN 202210056183A CN 114434917 B CN114434917 B CN 114434917B
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penetration
layer
composite material
graphene
adhesive
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CN114434917A (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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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Fluid Mechanics (AREA)
  • Aiming, Guidance, Guns With A Light Source, Armor, Camouflage, And Targets (AREA)
  • Laminated Bodies (AREA)

Abstract

An anti-penetration material, a preparation method and application thereof, wherein the anti-penetration material comprises the following components from outside to inside: the energy dissipation layer (5) comprises a composite material A and a composite material B, wherein the composite material A is a high-performance fiber-shear thickening fluid composite material, and the composite material B comprises at least one of high-performance fiber-graphene and high-performance fiber-graphene derivative composite material. The penetration-resistant material is a composite armor designed by comprehensively considering factors such as protection performance and maneuverability, 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 an anti-penetration material, a preparation method and application thereof.
Background
With the continuous improvement of penetration capability of modern weapons, higher requirements are put on the protection of helicopter armor and tank armor, and the weight of the bulletproof armor is also heavier and heavier. However, to ensure the maneuverability of the combat equipment, the contradiction between armor weight and its protection becomes a primary problem to be solved.
The metal bulletproof armor has the effect of effectively protecting against penetration of bullets, the thickness of the bulletproof steel needs to be continuously increased, and the maneuverability of combat equipment can be greatly sacrificed. Accordingly, researchers have developed armor for bulletproof of nonmetallic materials. Nonmetallic ceramic materials are widely used for replacing metal materials in bulletproof armor in recent years due to the characteristics of low density, high modulus and strong rigidity, and the hardness is not lost at high temperature. However, the application of ceramic materials to ballistic armor has been limited by the ease of overall fragmentation by the penetration of the bullets, and the inability to withstand successive penetration failures. The existing armor can not fully absorb the kinetic energy of the projectile when the projectile is resisted, and partial impact is still transmitted to the combat equipment, so that the impact is caused, and the operation stability of the combat equipment is affected. Therefore, the selection of multiple materials for compounding is a development trend for preparing modern bulletproof armor.
Currently, there are still many aspects of ballistic armor production that need to be improved, principally in terms of: (1) the protective requirements limit the weight reduction of armor; (2) the armor is not sufficiently resistant to continuous penetration failure; (3) The requirements of modern war on the protection of armor cannot be met; (4) The damping energy absorption of armor for ensuring the stable operation of the combat equipment is still to be improved.
In order to solve the above problems, systematic research and development on materials and integral structures of bulletproof armor are required.
Disclosure of Invention
The invention overcomes the defects and shortcomings in the background art, and provides an anti-penetration material, 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, the penetration-resistant material comprising, from outside to inside: the energy dissipation layer comprises a composite material A and a composite material B, wherein the composite material A is a high-performance fiber-shear thickening fluid composite material, and the composite material B comprises at least one of high-performance fiber-graphene and high-performance fiber-graphene derivative composite material; more preferably, a high performance fiber-graphene oxide composite is included.
The energy dissipation layer comprises a high-performance fiber-shear thickening fluid 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 fluid composite woven fabric composite material is soft and hard under the impact of a bullet, can absorb more impact energy, and increases the impact force dispersion area;
the graphene and the derivative thereof are used as a two-dimensional material, have good mechanical properties in the plane, and are favorable for transmitting stress waves generated by penetration of the projectile along the plane direction, so that impact energy is uniformly dispersed in the plane of the armor, and the protective performance is improved. And moreover, 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 energy transmission of the fiber, so that the energy transmission of bullet impact waves is facilitated, on one hand, the energy transmission between the fiber and the fiber can be improved, and on the other hand, the two-dimensional graphene plane in the thickness direction deflects under the action of penetration of a bullet, and the energy transmission between all layers of woven fabrics in the thickness direction can be improved.
Preferably, the high-performance fiber comprises at least one of aramid fiber II, aramid fiber III or ultra-high molecular weight polyethylene; the shear thickening fluid is SiO 2 -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 bullets, and plays roles of buffering, damping and energy absorption.
The rubber layer is designed between the energy dissipation layer and the energy absorption layer, and firstly, damping energy absorption and buffering and shock absorption are realized; secondly, the rigidity and the modulus of the rubber layer are smaller, and when the projectile penetrates into the rubber layer, the ballistic deflection of the projectile is easy to occur, so that the protection performance is enhanced.
Preferably, the rubber layer is provided therein with a cord fabric as a supporting skeleton, and the rubber includes at least one of natural rubber, butyl rubber or chloroprene rubber.
PreferablyThe ceramic layer is a ceramic splice plate formed by splicing ceramic whole plates or regular polygonal ceramic plates, and the material of the ceramic splice plate comprises Al 2 O 3 、SiC、B 4 C. BN or Si 3 N 4 At least one of (a) and (b); the supporting layer comprises carbon fibers; the constraint layer and the energy absorption layer comprise high-performance fibers; the upper and lower coatings include polyurea coatings. The polyurea coating has the characteristics of wear resistance and high hardness, and can effectively resist penetration of bullets.
Under the same technical conception, the invention also provides a preparation method of the penetration-resistant material, which comprises the following steps:
(1) Preparing an energy dissipation layer: the high-performance fiber (I) is subjected to dipping treatment by a shear thickening liquid and is dried to obtain a composite material A, the high-performance fiber (II) is subjected to dipping treatment by a presoaking adhesive solution containing graphene and/or graphene derivatives to obtain a composite material B, presoaking adhesives are coated on the surfaces of the composite material A and the composite material B, and after cross lamination, the composite material A and the composite material B are subjected to thermocompression bonding to obtain an energy dissipation layer;
(2) Sequentially bonding the constraint layer, the ceramic layer, the supporting 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) Polishing the anti-penetration material main body, and spraying upper and lower coatings to obtain the anti-penetration material.
Preferably, the preparation method of the pre-impregnated 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 presoaked adhesive solution, stirring, dispersing and performing ultrasonic vibration to obtain the presoaked adhesive solution containing the graphene and/or the graphene derivative, wherein the mass ratio of the presoaked adhesive to the graphene and/or the graphene derivative is (95:5) - (97.5:2.5); the presoaking 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 dispersing at least one of the components in SiO 2 The polyethylene glycol shear thickening liquid system is diluted by adding ethanol, and the dilution volume ratio is ethanol: the shear thickening liquid= (1-3): 1.
Preferably, the hot pressing temperature in the step (1) is 110-130 ℃ and the pressure is 10-15 MPa.
Preferably, the same kind of adhesive is selected in the step (1), the supporting layer in the step (2) is obtained by hot-press bonding after carbon fiber prepreg resin, the energy absorbing layer is obtained by hot-press bonding after high-performance fiber prepreg resin, and the prepreg adhesive and the prepreg resin comprise 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 interface cohesiveness and are not easy to cause interface debonding.
Preferably, the bonding in the step (2) is performed by using an adhesive, wherein the rubber layer is bonded with the adjacent energy dissipation layer and 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, so that the protection of the armor is ensured.
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 (3) spraying the upper and lower coatings comprises 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-resistant material, which is applied to bulletproof equipment.
Compared with the prior art, the invention has the beneficial effects that:
(1) The penetration-resistant material is a composite armor designed by comprehensively considering factors such as protection performance and maneuverability, 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 cross lamination and thermocompression bonding of the high-performance fiber and the composite material of the shearing thickening fluid, the graphene and the graphene derivative, and has higher energy transmission efficiency and can absorb and dissipate more energy compared with the energy dissipation layer obtained by thermocompression bonding of only single 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 used as a supporting framework, so that the damping energy absorption of the whole armor is improved, the impact generated by release of the kinetic energy of the projectile can be better absorbed, and the running stability of the combat equipment is ensured.
(4) The restraint layer is mainly used for preventing the ceramic layer from being broken and fragments from flying out, and improving the continuous penetration damage resistance of the armor.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic cross-sectional view of a penetration-resistant 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 (5) under-coating.
Detailed Description
The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments are shown, for the purpose of illustrating the invention, but the scope of the invention is not limited to the specific embodiments shown.
Unless defined otherwise, all technical and scientific terms 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 be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
Example 1: a step of
The preparation method of the penetration-resistant material comprises the following steps:
(1) The supporting layer is obtained by pre-impregnating a plurality of layers of carbon fiber woven cloth with resin and then bonding the layers by hot pressing, wherein the pre-impregnating 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 heat preservation and pressure maintaining for 30min under the conditions of 120-150 ℃ and 15-20 MPa.
(2) In SiO 2 Adding ethanol into the STF system of the polyethylene glycol system for dilution, wherein the dilution volume ratio is ethanol: STF=3:1, putting the aramid fiber II woven fabric into the solution for dipping treatment, taking out and drying for 8 hours at 60-100 ℃ to obtain the aramid fiber II/STF composite woven fabric.
Adding graphene into epoxy resin, stirring and dispersing uniformly, and performing ultrasonic oscillation for 30min to obtain graphene-containing epoxy resin dispersion liquid after uniform dispersion, wherein the mass ratio of the graphene to the epoxy resin is: =95:5; and (3) carrying out impregnation treatment on the aramid fiber III fiber woven cloth by using epoxy resin dispersion liquid containing graphene to obtain the aramid fiber III/graphene composite woven cloth, wherein the epoxy resin dispersion liquid accounts for 40% -50% of the total weight of the fiber prepreg.
Coating epoxy resin adhesive on the surfaces of the aramid fiber II/STF composite woven cloth and the aramid fiber III/graphene composite woven cloth, stacking the layers, and preserving heat and pressure for 20 minutes 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-absorbing layer is obtained by pre-impregnating a plurality of layers of ultra-high molecular weight polyethylene fiber woven cloth with resin and then bonding the layers together through hot pressing, wherein the pre-impregnating resin is epoxy resin, the mass ratio of the epoxy resin to the second fiber composite layer is 25-30%, and the energy-absorbing layer with the thickness of 5mm is obtained by heat preservation and pressure maintaining for 30min under the conditions of 120-150 ℃ and 18-25 MPa.
(4) Sequentially stacking a constraint layer, a ceramic layer, a supporting layer, an energy dissipation layer, a rubber layer and an energy absorption layer, wherein the constraint 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 neoprene layer with the thickness of 5mm, and a cord fabric is arranged in the rubber layer to serve as a reinforcing framework; the rubber layer is bonded with the adjacent energy dissipation layer and energy absorption layer by adopting double-coating adhesive, the interfaces of the other layers are bonded by epoxy resin, and after standing for 12 hours at room temperature, the rubber layer is subjected to hot pressing and compounding in an autoclave, and the hot pressing process conditions are as follows: the temperature is controlled to be 110-120 ℃, the pressure is controlled to be 2-2.5 MPa, the heat preservation and the pressure maintaining are carried out for 1h, the armor main body is obtained, the surface of the armor main body is polished and flattened by a grinding wheel, and then polyurea coatings with the thickness of 0.5mm are respectively sprayed on the upper surface and the lower surface of the armor main body.
An anti-penetration material comprising, from the outside to the inside: the energy dissipation layer 5 comprises an aramid fiber II/STF composite woven fabric and an 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-resistant material of example 1; as can be seen from the figure, the upper coating 1, the constraint layer 2, the ceramic layer 3, the supporting layer 4, the energy dissipation layer 5, the energy absorption layer 7 and the lower coating 8 are sequentially arranged in sequence and are compounded into the penetration-resistant material.
Example 2:
example 2 differs from example 1 in that SiO 2 The volume ratio of STF system to ethanol dilution of the polyethylene glycol system is 1:1.
Example 3:
embodiment 3 differs from embodiment 1 in that graphene is graphene oxide.
Tests show that SiO 2 The anti-puncture 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; the graphene oxide has better combination with a fiber interface due to the existence of polar groups on the surface, and the mechanical property of the graphene oxide is superior to that of graphene.

Claims (11)

1. A penetration-resistant material, comprising, from outside to inside: the energy dissipation layer (5) comprises a composite material A and a composite material B, wherein the composite material A is a high-performance fiber-shear thickening fluid composite material, and the composite material B comprises at least one of high-performance fiber-graphene and high-performance fiber-graphene derivative composite material; the high-performance fiber comprises at least one of aramid fiber II, aramid fiber III or ultra-high molecular weight polyethylene, the shear thickening fluid is a SiO 2-polyethylene glycol system, and the composite material A and the composite material B are laminated in a cross manner; a rubber layer (6) is arranged between the energy dissipation layer (5) and the energy absorption layer (7).
2. The penetration-resistant material according to claim 1, characterized in that a cord fabric is provided in the rubber layer (6) as a supporting skeleton, the rubber comprising at least one of natural rubber, butyl rubber or neoprene.
3. The penetration-resistant material according to any one of claims 1 to 2, wherein the ceramic layer (3) is a ceramic plate or a ceramic splice plate formed by splicing regular polygonal ceramic plates, and comprises Al 2 O 3 、SiC、B 4 C. BN or Si 3 N 4 At least one of (a) and (b); 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.
4. A method of preparing the penetration-resistant material of any one of claims 1 to 3, comprising the steps of:
(1) Preparing an energy dissipation layer: the high-performance fiber (I) is subjected to dipping treatment by a shear thickening liquid and is dried to obtain a composite material A, the high-performance fiber (II) is subjected to dipping treatment by a presoaking adhesive solution containing graphene and/or graphene derivatives to obtain a composite material B, presoaking adhesives are coated on the surfaces of the composite material A and the composite material B, and after cross lamination, the composite material A and the composite material B are subjected to thermocompression bonding to obtain an energy dissipation layer;
(2) Sequentially bonding the constraint layer, the ceramic layer, the supporting 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) Polishing the anti-penetration material main body, and spraying upper and lower coatings to obtain the anti-penetration material.
5. The method of preparing the penetration-resistant material according to claim 4, wherein the preparation method of the prepreg adhesive solution containing graphene and/or a graphene derivative in the step (1) is as follows: adding graphene and/or a graphene derivative into a presoaked adhesive solution, stirring, dispersing and performing ultrasonic vibration to obtain the presoaked adhesive solution containing the graphene and/or the graphene derivative, wherein the mass ratio of the presoaked adhesive to the graphene and/or the graphene derivative is (95:5) - (97.5:2.5); the presoaking adhesive solution containing the graphene and/or the graphene derivative accounts for 30-50% of the total weight of the composite material B.
6. The method of preparing a penetration-resistant material as recited in claim 4, wherein said shear thickening fluid is prepared by mixing at least one of the components of SiO 2 The polyethylene glycol shear thickening liquid system is diluted by adding ethanol, and the dilution volume ratio is ethanol: the shear thickening liquid= (1-3): 1.
7. The method of producing an anti-penetration material according to claim 4 or 5, wherein the hot pressing temperature in step (1) is 110 to 130 ℃ and the pressure is 10 to 15MPa.
8. The method of manufacturing an anti-penetration material according to claim 4 or 5, wherein the prepreg adhesive in step (1) is the same, the support layer in step (2) is obtained by thermal compression bonding after carbon fiber prepreg resin, the energy absorbing layer is obtained by thermal compression bonding after high-performance fiber prepreg resin, and the prepreg adhesive and the prepreg resin comprise at least one of epoxy resin, phenolic resin and polyurethane.
9. The method of preparing an anti-penetration material according to claim 4, wherein the bonding in step (2) is performed by using an adhesive, wherein the rubber layer is bonded with the adjacent energy dissipation layer and energy absorption layer by using a double-coated adhesive, and the adhesive comprises at least one of epoxy resin, phenolic resin, polyurethane, polyvinyl acetate, ethylene-vinyl acetate copolymer, and polyvinyl acetal.
10. The method for producing an anti-penetration material according to claim 4, wherein the hot-pressing temperature in the step (2) is controlled to be 110 to 120 ℃ and the pressure is controlled to be 2 to 2.5MPa; and (3) spraying the upper and lower coatings comprises spraying polyurea coatings on the upper surface and the lower surface of the armor main body.
11. Use of a penetration-resistant material according to any of claims 1-3, in ballistic-resistant equipment.
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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
Publication number Priority date Publication date Assignee Title
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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