CN114957989A - Bulletproof composite material and preparation method thereof - Google Patents
Bulletproof composite material and preparation method thereof Download PDFInfo
- Publication number
- CN114957989A CN114957989A CN202210563235.6A CN202210563235A CN114957989A CN 114957989 A CN114957989 A CN 114957989A CN 202210563235 A CN202210563235 A CN 202210563235A CN 114957989 A CN114957989 A CN 114957989A
- Authority
- CN
- China
- Prior art keywords
- layer
- composite material
- bullet
- fiber
- fibers
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002131 composite material Substances 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims description 22
- 239000000835 fiber Substances 0.000 claims abstract description 173
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 claims abstract description 77
- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 claims abstract description 75
- 239000004642 Polyimide Substances 0.000 claims abstract description 61
- 229920001721 polyimide Polymers 0.000 claims abstract description 61
- 239000000463 material Substances 0.000 claims abstract description 38
- 239000010410 layer Substances 0.000 claims description 188
- 229920005989 resin Polymers 0.000 claims description 42
- 239000011347 resin Substances 0.000 claims description 42
- 239000011159 matrix material Substances 0.000 claims description 28
- 229920005992 thermoplastic resin Polymers 0.000 claims description 23
- 239000000805 composite resin Substances 0.000 claims description 18
- 238000000465 moulding Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- 229920005749 polyurethane resin Polymers 0.000 claims description 9
- 230000002787 reinforcement Effects 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 4
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 4
- 229920005668 polycarbonate resin Polymers 0.000 claims description 4
- 239000004431 polycarbonate resin Substances 0.000 claims description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 4
- 230000002708 enhancing effect Effects 0.000 claims description 2
- 239000002344 surface layer Substances 0.000 claims description 2
- 239000003292 glue Substances 0.000 claims 2
- 239000003733 fiber-reinforced composite Substances 0.000 abstract description 6
- 229920010741 Ultra High Molecular Weight Polyethylene (UHMWPE) Polymers 0.000 abstract 1
- 238000010521 absorption reaction Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 229920005990 polystyrene resin Polymers 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 5
- 239000012792 core layer Substances 0.000 description 5
- 230000035515 penetration Effects 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- 238000007731 hot pressing Methods 0.000 description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- 230000000149 penetrating effect Effects 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- -1 styrene free radical Chemical class 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 229920000271 Kevlar® Polymers 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000002591 computed tomography Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000013016 damping Methods 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000002657 fibrous material Substances 0.000 description 2
- 239000004761 kevlar Substances 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002313 adhesive film Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000013013 elastic material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000013521 mastic Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 239000012209 synthetic fiber Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 230000008733 trauma Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
- C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/30—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core
- B29C70/34—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core and shaping or impregnating by compression, i.e. combined with compressing after the lay-up operation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/54—Component parts, details or accessories; Auxiliary operations, e.g. feeding or storage of prepregs or SMC after impregnation or during ageing
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F41—WEAPONS
- F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
- F41H1/00—Personal protection gear
- F41H1/02—Armoured or projectile- or missile-resistant garments; Composite protection fabrics
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F41—WEAPONS
- F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
- F41H1/00—Personal protection gear
- F41H1/04—Protection helmets
- F41H1/08—Protection helmets of plastics; Plastic head-shields
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F41—WEAPONS
- F41H—ARMOUR; ARMOURED TURRETS; ARMOURED OR ARMED VEHICLES; MEANS OF ATTACK OR DEFENCE, e.g. CAMOUFLAGE, IN GENERAL
- F41H5/00—Armour; Armour plates
- F41H5/02—Plate construction
- F41H5/04—Plate construction composed of more than one layer
- F41H5/0471—Layered armour containing fibre- or fabric-reinforced layers
- F41H5/0478—Fibre- or fabric-reinforced layers in combination with plastics layers
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Composite Materials (AREA)
- Mechanical Engineering (AREA)
- Ceramic Engineering (AREA)
- Aiming, Guidance, Guns With A Light Source, Armor, Camouflage, And Targets (AREA)
- Laminated Bodies (AREA)
Abstract
The invention relates to a high-strength high-modulus Polyimide (PI) fiber/ultrahigh molecular weight polyethylene (UHMWPE) fiber bulletproof composite material, which is characterized in that PI fibers and UHMWPE fibers are matched for use, a layer structure of a bullet facing layer, an interface layer, a middle layer, an interface layer and a backfire layer is adopted by reasonably designing the structure, PI fiber reinforced composite materials are paved on the bullet facing layer and the backfire layer, and UHMWPE fiber reinforced composite materials are paved on the middle layer.
Description
Technical Field
The invention relates to a bulletproof composite material, in particular to a polyimide fiber/ultra-high molecular weight polyethylene fiber bulletproof composite material and a preparation method thereof.
Background
The successful development of Kevlar (Kevlar) which is a para-aramid polyamide fiber by Dupont in the United states at the end of the 60 th century brings revolutionary leap for the field of individual bulletproof. Dyneema and Spectra ultra high molecular weight polyethylene fibers were developed in the 80 th century by DSM, Dyneema, in the Netherlands, and by Allied Signal, in the United states (now Honeywell, Inc.). Provides more choices for lightweight high-performance bulletproof materials in the field of individual bulletproof, and the high-performance organic synthetic fibers become the dominant bulletproof material used by modern individual bulletproof equipment. In the 70's of the 20 th century, polymer composites based on high performance chemical fibers and resins began to be used in the preparation of ballistic helmet shells. The helmet greatly reduces the weight of the helmet while ensuring the ballistic protection performance, and gradually replaces the traditional metal material. At present, bulletproof helmets and bulletproof clothes of army equipment in various countries are mainly developed by polymer composite materials.
CN106905652A relates to a bulletproof composite material and a preparation method thereof, wherein the bulletproof composite material is obtained by vacuum curing after a plurality of layers of UHMWPE fiber cloth are soaked in modified polystyrene resin prepolymer; the modified polystyrene resin prepolymer is prepared by heating and uniformly stirring styrene and EVA particles, adding an initiator and a crosslinking agent, and carrying out prepolymerization. The V50 value of the bulletproof composite material prepared by the invention can reach 623m/s, the bulletproof composite material has good ballistic penetration resistance and light weight, the preparation method is simple and easy to implement, the cost is low, and the bulletproof composite material is convenient for one-step molding of large-size and special-shaped pieces and has good application prospect, such as being used for preparing soft bulletproof clothes, bulletproof armor and the like.
CN108316016A relates to the technical field of high-resistance bulletproof composite materials, and discloses an ultrahigh molecular weight polyethylene fiber bulletproof composite material and a preparation method thereof, wherein the bulletproof composite material is formed by compounding modified polystyrene resin and UHMWPE fibers, and the modified polystyrene resin is prepared by modifying polystyrene resin by using ethylene-vinyl acetate copolymer EVA with high flexibility, elasticity and filler compatibility; the polymer obtained by polymerizing the monomer styrene free radical of the polystyrene resin is colorless and transparent, has high rigidity, and can improve the wettability of the modified resin to fibers. The bulletproof composite material has the advantages of low density, high specific strength, high specific modulus, good damping property, fatigue resistance, good environmental adaptability and the like, and meets the bulletproof requirement. The preparation method has the advantages of simple steps, strong operability and batch production.
The most important of the performance requirements of individual ballistic armour is ballistic protection, i.e. whether it will prevent penetration by the intended threat projectile. Ballistic limits describe the relationship between the velocity of impact of a projectile on a ballistic material or harness and the probability of penetration through the ballistic material or harness. The method can be used for characterizing the bulletproof performance of the bulletproof material on certain bullets and evaluating the penetration capacity of kinetic energy bullets on certain materials. The most common ballistic limit at present is V 50 I.e. the speed at which the probability of penetration is 50%. When the areal densities of the target plates are the same or similar, V can be compared 50 The value (unit: m/s) is used for measuring the bulletproof performance of the two. When the areal density of the target plate varies greatly, the ballistic performance per areal density needs to be calculated from the specific absorption energy. The specific absorption energy is calculated as follows:
in the formula: SEA is the specific absorption energy (unit: J.m) of the target plate 2 /kg); m is the mass (unit: kg) of the projectile; AD is the areal density (unit: kg/m) of the target plate 2 )。
Some ballistic resistant harnesses should also take into account non-penetrating damage because the ballistic resistant harness deforms and bulges while protecting the projectile. Individual ballistic equipment should meet certain non-penetrating blunt trauma protection requirements, in addition to meeting the ballistic limits specified by the standards, as characterized by the depth of the crater left on the mastic padding behind the body armor sample (the depth of protrusion of the back).
Therefore, light weight, high ballistic limit speed and low dorso-convexity are the three most important indexes in the field of individual ballistic protection engineering. The fiber reinforced resin matrix composite material has the characteristics of low density, high specific strength, high specific modulus, high specific energy absorption, high designability and the like, and is widely applied to the field of individual ballistic protection engineering. Ultra-high molecular weight polyethylene fibers (UHMWPE) due to its lower density (0.97 g/cm) 3 ) Higher breaking strength and good toughness are favored in the ballistic field. However, good toughness, while bringing a high ballistic limit, also allows the UHMWPE fiber reinforced resin based composite to develop a great backfolding during use as a ballistic material. Meanwhile, the UHMWPE has poor high temperature resistance, and the application range of the UHMWPE is limited to a certain extent. The high-strength high-modulus polyimide fiber has the characteristics of high strength, high modulus, high temperature resistance and high fracture toughness, and has the characteristics of low deformation rate and small back bulge compared with UHMWPE fiber.
CN 108673984A discloses a bulletproof composite material, which is a resin-based composite material taking polyimide fibers as a reinforcement, wherein the mass percentage of the polyimide fibers is 60-90%, and the mass percentage of a resin matrix is 10-40%. The polyimide fiber is modified fiber subjected to interface treatment by adopting an inert modifier, and the inert modifier is formed by mixing aqueous thermoplastic polyurethane and aqueous polyolefin resin according to a certain proportion. The invention also discloses a preparation method and application of the bulletproof composite material. The invention adopts polyimide fiber as reinforcement, is soaked in matrix resin according to a certain arrangement mode through special interface treatment, and is compounded with the matrix resin through a specific compounding process, so that the prepared bulletproof composite material has higher tensile strength and tensile modulus, has good high and low temperature resistance and light weight, also has good fire resistance and spinnability, and is suitable for being prepared into soft bulletproof clothes and bulletproof armor materials with strong wearing comfort.
The composite material target plate with the hybrid structure is prepared by simultaneously adopting the PI fiber and the UHMWPE fiber, and the PI fiber and the UHMWPE fiber can fully play a synergistic effect by reasonably designing the hybrid proportion and the hybrid layering structure, thereby meeting the requirements of the composite material on high-ratio energy absorption and low back projection.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a hybrid fiber reinforced resin matrix composite material and a preparation method thereof aiming at the defects in the prior art, the composite material has the advantages of light weight, good bulletproof effect, small back convex height, good environment resistance and the like, and the preparation method has the characteristics of simplicity, convenience, practicability, operability, strong designability and the like.
According to the invention, through the matching use of the high-strength high-modulus PI fibers and the UHMWPE fibers, the performance advantages of the two fibers are fully exerted, the back convex height can be limited under the condition of ensuring a higher SEA value, and the protection effect is effectively improved. The PI fiber is an important use form of polyimide material, and inherits all excellent characteristics of polyimide. The first bulletproof barrier is made of the PI fiber material with high orientation, the elastic sheet entering the material at high speed is subjected to damping motion by utilizing the characteristics of high strength and high modulus, and the characteristics of high temperature resistance and high specific absorption energy of the PI material can be utilized. The intermediate layer uses UHMWPE material with proper thickness, and the characteristic of high elastic track limit is exerted to the maximum extent. And meanwhile, a layer specially used for limiting the back convex depth is arranged below the middle layer, preferably PI fibers, so that the non-penetrating damage of the bulletproof composite material is enhanced.
Meanwhile, in the preparation of the composite material, the high-strength high-modulus PI fibers and the ultra-high molecular weight polyethylene fibers with respective high orientation are staggered at a specific angle, and then the two layers of fibers are bonded by resin by hot pressing to form an interface. The high-strength high-modulus polyimide fibers and the ultra-high molecular weight polyethylene fibers interact at the interface to form an interface layer with high impact resistance and cutting resistance in a staggered mode, and the bulletproof performance is further improved. Meanwhile, the interface layer formed between the middle layer and the back elastic layer can also greatly offset the depth expansion of the back convex height. Furthermore, the problem of poor surface adhesion caused by smooth surface of UHMWPE fibers and no polar groups on a macromolecular main chain can be well solved by performing thermoplastic resin film enhancement treatment on the interface layer; and the reinforcing treated resin resolidifies the interwoven PI fibers and UHMWPE fibers, and the interface bonding strength is increased. In addition, the relative thickness between each layer is controlled to achieve the effect of optimizing both density and strength.
Specifically, the invention provides a polyimide fiber/ultra-high molecular weight polyethylene fiber bulletproof composite material, which has the following structure:
include in proper order as infrastructure, meet bullet layer, interface layer, intermediate level, interface layer, the layer of playing on the back, its characterized in that:
the reinforced fibers of the bullet facing layer and the bullet backing layer are high-strength high-modulus polyimide fibers;
taking the thickness of the middle layer as a reference, the total thickness of the bullet facing layer and the bullet backing layer is 0.2-1 compared with the thickness of the middle layer; the missile-facing layer, the middle layer and the missile-backing layer are all made by unidirectional arrangement in a fiber surface and orthogonal laying between layers, and the interface layer is an interface formed by the surface layers of two types of fibers and a thermoplastic resin film introduced for enhancing the bonding strength of the interface at the junction.
The bulletproof composite material is characterized in that the composition of the bullet facing layer and the composition of the bullet backing layer are the same, the bulletproof composite material is a resin matrix composite material taking high-strength and high-modulus polyimide fibers as a reinforcement, and the middle layer is a resin matrix composite material taking ultra-high molecular weight polyethylene fibers as a reinforcement.
In some preferred embodiments, the thickness ratio of the bullet facing layer to the bullet backing layer is 1: 0.9-1.
In some preferred embodiments, the matrix of the resin-based composite material is one or more thermoplastic resins selected from polyurethane resins, polyvinyl butyral ester resins, styrene butadiene block copolymers, and polycarbonate resins.
In some preferred embodiments, in the resin-based composite material of the ballistic layer and the back ballistic layer, the proportion of the high-strength high-modulus polyimide fiber is 70-90%, and the proportion of the resin matrix is 10-30%.
In some preferred embodiments, the resin-based composite material of the middle layer comprises 70% to 90% of ultra-high molecular weight polyethylene fibers and 10% to 30% of resin matrix.
In some preferred embodiments, the high-strength high-modulus polyimide has a tensile strength of 3.4GPa or more and a tensile modulus of 110GPa or more.
In some preferred embodiments, the ultra-high molecular weight polyethylene fibers have a tensile strength of 3.2GPa or more and a tensile modulus of 100GPa or more.
The second aspect of the invention also provides a preparation method of the polyimide fiber/polyethylene fiber bulletproof composite material, which is characterized by comprising the following steps of:
(1) sequentially and alternately arranging prepregs with respective high-orientation polyimide fibers/polyethylene fibers in a unidirectional arrangement mode according to a fiber arrangement direction of 0 DEG/90 DEG, and additionally laying a layer of thermoplastic resin film at the interface between the bullet facing layer and the middle layer and the interface between the middle layer and the back bullet layer to reinforce the interface;
(2) and (3) placing the laid prepreg into a mould, and carrying out hot-press molding at the hot-press temperature of 70-130 ℃ under the pressure of 0.5-5 MPa for 0.1-1 hour.
In some preferred embodiments, the thermoplastic resin is one or more of a polyurethane resin, a polyvinyl butyral ester resin, a styrene butadiene block copolymer, and a polycarbonate resin.
In some preferred embodiments, the thermoplastic resin film is in the form of one or more of a film, a web, or a reticulated film.
In some preferred embodiments, the interface is subjected to the enhancement treatment by the following specific processes: the thickness of the resin film is controlled within 0.1mm, and the surface density is controlled at 100g/m 2 The area of the resin film is consistent with the area of the laying layer of the prepreg, and the molding temperature of the resin film is controlled within a hot-pressing temperature interval.
The bonding strength of the formed resin film ensures the integrity of the composite material target plate after being impacted by the bullet with a certain speed in a target use scene, namely, the target plate is separated into a plurality of pieces due to no obvious layering at the interface, and the potential safety hazard is avoided.
Compared with the prior art, the invention has the following technical effects:
according to the invention, through the matching use of the high-strength high-modulus PI fiber and the UHMWPE fiber, the performance advantages of the two fibers are fully exerted, the back convex height can be limited under the condition of ensuring a higher SEA value, and the protection effect is effectively improved. By reasonably designing the layer structure, adopting the layer structure of the bullet facing layer, the interface layer, the middle layer, the interface layer and the back bullet layer, laying the high-strength high-modulus PI fiber reinforced composite material on the bullet facing layer and the back bullet layer, and laying the UHMWPE fiber reinforced composite material on the middle layer, the high modulus advantage of PI fiber and the high ratio energy absorption advantage of UHMWPE fiber can be fully exerted, and the back convex height can be effectively limited while the composite material is ensured to have higher specific energy absorption value. In addition, when the composite material is prepared, the high-strength high-modulus polyimide fibers with high orientation and the ultra-high molecular weight polyethylene fibers are staggered at a specific angle, and then the two layers of fibers are bonded through resin by hot pressing to form an interface. The high-strength high-modulus polyimide fibers and the ultra-high molecular weight polyethylene fibers interact at the interface to form an interface layer with high impact resistance and cutting resistance in a staggered mode, and the bulletproof performance is further improved. Meanwhile, the reinforced interface layer can further eliminate the internal stress generated by different thermal dimensional behaviors of the two fiber materials in the forming process of the composite material, avoid the warping phenomenon and ensure the stability of the composite material in the protection process. The composite material prepared by the invention adopts a 0 degree/90 degree UD reinforcing structure, and the orthogonal arrangement of fibers in the structure is favorable for the transmission of stress waves, so that the two fibers can better play a synergistic effect in the protection process.
The thickness of the resin film is controlled within 0.1mm, and the surface density is controlled at 100g/m 2 The area of the resin film is consistent with the area of the laying layer of the prepreg, and the molding temperature of the film is controlled within a hot-pressing temperature interval. The adhesive strength of the adhesive film can ensure the integrity of the composite material target plate after being impacted by a bullet with a certain speed in a target use scene, namely, the target plate is separated into two parts due to no obvious layering at the interfaceAnd (4) multiple blocks.
Meanwhile, the problem of poor surface adhesion caused by smooth surface of UHMWPE fibers and no polar group on a macromolecule main chain can be well solved by the enhancement treatment of the interface layer, and meanwhile, the strength of the interface layer can be further adjusted through the form of the thermoplastic resin, so that the contribution of interweaving interface layering to energy absorption can be exerted while the bonding strength of the interface layer is ensured, and the bulletproof performance is further improved.
Drawings
FIG. 1 is a schematic structural design diagram of a PI fiber and UHMWPE fiber hybrid reinforced resin matrix composite material of the present invention.
FIG. 2 is an apparent topography after a backface-like shooting experiment of the composite material target plate in example 2 of the present invention.
FIG. 3 is the internal CT scan results after the backface-projection experiment of the composite target in example 2 of the present invention.
FIG. 4 shows the surface morphology of the projectile after the backface-projection shooting experiment of the composite target plate in comparative example 2 of the present invention.
Detailed Description
The present invention is described in more detail below to facilitate an understanding of the present invention.
In the description herein, references to the description of "one embodiment," "another embodiment," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment is included in at least one embodiment of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Moreover, various embodiments or examples and features of various embodiments or examples described in this specification can be combined and combined by one skilled in the art without being mutually inconsistent.
The polyimide fiber/polyethylene fiber bulletproof composite material is structurally compounded into a layered structure. The schematic diagram is shown in fig. 1, and the elastic material comprises an elastic facing layer, an interface layer, an intermediate layer, an interface layer and a back elastic layer in sequence. The bulletproof material has wide application in body bulletproof equipment, including light bulletproof clothes, bulletproof plates or bulletproof helmets. Wherein the bullet facing layer and the bullet backing layer are made of high-strength high-modulus PI fiber reinforced composite materials, and the middle layer is made of UHMWPE fiber reinforced composite materials.
The UHMWPE fiber used by the invention generally has the characteristics of high specific strength and high specific modulus, and is particularly characterized in that the fiber density is low, and the density is 0.97-0.98g/cm 3 Can float on the water surface; high elongation at break, high work at break, and strong ability to absorb energy, thus having outstanding impact resistance and cut resistance.
Optionally, for specific needs, other high-strength and high-modulus organic fibers and UHMWPE fibers are adopted to perform structural design based on the same principle, and the same effect can be achieved, such as PBO fibers, aramid III fibers, and the like.
The starting materials used in the preparation process of the present invention are essentially commercially available.
The following is a more detailed description of embodiments of the invention.
Example 1
A polyimide fiber/ultra-high molecular weight polyethylene fiber bulletproof composite material adopts the following preparation method, and comprises the following steps:
(1) sequentially and alternately arranging prepregs with respective high-orientation polyimide fibers/ultrahigh molecular weight polyethylene fibers in a unidirectional arrangement mode according to a fiber arrangement direction of 0/90 degrees to sequentially form a bullet facing layer, an intermediate layer and a back bullet layer, and paving a layer of thermoplastic resin film at the interface between the bullet facing layer and the intermediate layer and between the intermediate layer and the back bullet layer to reinforce the interface to form an interface layer, wherein the thermoplastic resin is polyurethane resin;
(2) and (3) placing the laid prepreg into a mould, and carrying out hot-press molding at the hot-press temperature of 120 ℃, under the pressure of 1MPa for 0.3 hour to obtain the polyimide fiber/ultra-high molecular weight polyethylene fiber bulletproof composite material.
A polyimide fiber/ultra-high molecular weight polyethylene fiber bulletproof composite material comprises a bullet facing layer, a middle layer and a back bullet layer, wherein the thickness ratio of the bullet facing layer to the middle layer is 0.1: 1: 0.1; in the resin-based composite material of the bullet facing layer and the bullet backing layer, the mass percentage of the high-strength high-modulus polyimide fibers is 85%, the mass percentage of the resin matrix is 15%, and in the resin-based composite material of the middle layer, the mass percentage of the ultrahigh molecular weight polyethylene fibers is 85%, and the mass percentage of the resin matrix is 15%.
Example 2
A polyimide fiber/ultra-high molecular weight polyethylene fiber bulletproof composite material adopts the following preparation method, and comprises the following steps:
(1) sequentially and alternately arranging prepregs with respective high-orientation polyimide fibers/ultrahigh molecular weight polyethylene fibers in a unidirectional arrangement mode according to a fiber arrangement direction of 0/90 degrees to sequentially form a bullet facing layer, an intermediate layer and a back bullet layer, and paving a layer of thermoplastic resin film at the interface between the bullet facing layer and the intermediate layer and between the intermediate layer and the back bullet layer to reinforce the interface to form an interface layer, wherein the thermoplastic resin is polyurethane resin;
(2) and (3) placing the laid prepreg into a mould, and carrying out hot-press molding at the hot-press temperature of 120 ℃, under the pressure of 1MPa for 0.3 hour to obtain the polyimide fiber/ultra-high molecular weight polyethylene fiber bulletproof composite material.
A polyimide fiber/ultra-high molecular weight polyethylene fiber bulletproof composite material comprises a bullet facing layer, a middle layer and a back bullet layer, wherein the thickness ratio of the bullet facing layer to the middle layer is 0.125: 1: 0.125; in the resin-based composite material of the bullet facing layer and the bullet backing layer, the mass percentage of the high-strength high-modulus polyimide fibers is 85%, the mass percentage of the resin matrix is 15%, and in the resin-based composite material of the middle layer, the mass percentage of the ultrahigh molecular weight polyethylene fibers is 85%, and the mass percentage of the resin matrix is 15%.
Example 3
A polyimide fiber/ultra-high molecular weight polyethylene fiber bulletproof composite material adopts the following preparation method, and comprises the following steps:
(1) sequentially and alternately arranging prepregs with respective high-orientation polyimide fibers/ultrahigh molecular weight polyethylene fibers in a unidirectional arrangement mode according to a fiber arrangement direction of 0/90 degrees to sequentially form a bullet facing layer, an intermediate layer and a back bullet layer, and paving a layer of thermoplastic resin film at the interface between the bullet facing layer and the intermediate layer and between the intermediate layer and the back bullet layer to reinforce the interface to form an interface layer, wherein the thermoplastic resin is polyurethane resin;
(2) and (3) placing the laid prepreg into a mould, and carrying out hot-press molding at the hot-press temperature of 120 ℃, under the pressure of 1MPa for 0.3 hour to obtain the polyimide fiber/ultra-high molecular weight polyethylene fiber bulletproof composite material.
A polyimide fiber/ultra-high molecular weight polyethylene fiber bulletproof composite material comprises a bullet facing layer, an intermediate layer and a back bullet layer, wherein the thickness ratio of the bullet facing layer to the intermediate layer is 0.25: 1: 0.25; in the resin-based composite material of the bullet facing layer and the bullet backing layer, the mass percentage of the high-strength high-modulus polyimide fibers is 85%, the mass percentage of the resin matrix is 15%, and in the resin-based composite material of the middle layer, the mass percentage of the ultrahigh molecular weight polyethylene fibers is 85%, and the mass percentage of the resin matrix is 15%.
Example 4
A polyimide fiber/ultra-high molecular weight polyethylene fiber bulletproof composite material adopts the following preparation method, and comprises the following steps:
(1) sequentially and alternately arranging prepregs with respective high-orientation polyimide fibers/ultrahigh molecular weight polyethylene fibers in a unidirectional arrangement mode according to a fiber arrangement direction of 0/90 degrees to sequentially form a bullet facing layer, an intermediate layer and a back bullet layer, and paving a layer of thermoplastic resin film at the interface between the bullet facing layer and the intermediate layer and between the intermediate layer and the back bullet layer to reinforce the interface to form an interface layer, wherein the thermoplastic resin is polyurethane resin;
(2) and (3) placing the laid prepreg into a mould, and carrying out hot-press molding at the hot-press temperature of 120 ℃, under the pressure of 1MPa for 0.3 hour to obtain the polyimide fiber/ultra-high molecular weight polyethylene fiber bulletproof composite material.
A polyimide fiber/ultra-high molecular weight polyethylene fiber bulletproof composite material comprises an impact layer, an intermediate layer and a back elastic layer, wherein the thickness ratio of the impact layer to the back elastic layer is 0.5: 1: 0.5; in the resin-based composite material of the bullet facing layer and the bullet backing layer, the mass percentage of the high-strength high-modulus polyimide fibers is 85%, the mass percentage of the resin matrix is 15%, and in the resin-based composite material of the middle layer, the mass percentage of the ultrahigh molecular weight polyethylene fibers is 85%, and the mass percentage of the resin matrix is 15%.
Example 5
A polyimide fiber/ultra-high molecular weight polyethylene fiber bulletproof composite material adopts the following preparation method, and comprises the following steps:
(1) sequentially and alternately arranging prepregs with respective high-orientation polyimide fibers/ultrahigh molecular weight polyethylene fibers in a unidirectional arrangement manner according to a fiber arrangement direction of 0/90 degrees to sequentially form an elastic layer, an intermediate layer and a back elastic layer, and paving a layer of thermoplastic resin net film at the interface between the elastic layer and the intermediate layer and between the intermediate layer and the back elastic layer to reinforce the interface to form an interface layer, wherein the thermoplastic resin is polyurethane resin;
(2) and (3) placing the laid prepreg into a mould, and performing hot press molding at the hot press temperature of 120 ℃, under the pressure of 1MPa for 0.3 hour to obtain the polyimide fiber/ultra-high molecular weight polyethylene fiber bulletproof composite material.
A polyimide fiber/ultra-high molecular weight polyethylene fiber bulletproof composite material comprises a bullet facing layer, an intermediate layer and a back bullet layer, wherein the thickness ratio of the bullet facing layer to the intermediate layer is 0.25: 1: 0.25; in the resin-based composite material of the bullet facing layer and the bullet backing layer, the mass percentage of the high-strength high-modulus polyimide fibers is 85%, the mass percentage of the resin matrix is 15%, and in the resin-based composite material of the middle layer, the mass percentage of the ultrahigh molecular weight polyethylene fibers is 85%, and the mass percentage of the resin matrix is 15%.
Comparative example 1
A polyimide fiber bulletproof composite material adopts the following preparation method, and comprises the following steps:
(1) prepregs in which polyimide fibers each having a high orientation are unidirectionally arranged are sequentially arranged in a staggered manner in a fiber arrangement direction of 0/90 °.
(2) And (3) placing the laid prepreg into a mould, and carrying out hot press molding at the hot press temperature of 125 ℃ under the pressure of 1MPa for 0.3 hour to obtain the polyimide fiber bulletproof composite material.
A polyimide fiber bulletproof composite material is characterized in that the mass percentage of high-strength and high-modulus polyimide fibers is 85%, and the mass percentage of a resin matrix is 15%.
Comparative example 2
An ultra-high molecular weight polyethylene fiber bulletproof composite material adopts the following preparation method, which comprises the following steps:
(1) prepregs in which respective highly oriented ultrahigh molecular weight polyethylene fibers are unidirectionally arranged are sequentially arranged in a staggered manner in a fiber arrangement direction of 0/90 °.
(2) And (3) placing the laid prepreg into a mould, and carrying out hot-press molding at the hot-press temperature of 120 ℃, under the pressure of 1MPa for 0.3 hour to obtain the ultrahigh molecular weight polyethylene fiber bulletproof composite material.
The bulletproof composite material of the ultrahigh molecular chain polyethylene fiber comprises 85% of the ultrahigh molecular chain polyethylene fiber by mass and 15% of a resin matrix by mass.
Comparative example 3
With reference to example 2, the parameters and processes were the same except that no interface enhancement treatment was performed between the ballistic layer and the intermediate layer, and between the intermediate layer and the backflastic layer.
TABLE 1
As can be seen from the data in Table 1, compared with the comparative ratio, the polyimide fiber/ultrahigh molecular weight polyethylene fiber composite material prepared by the invention can fully exert the synergistic effect of two fibers, effectively reduce the back bulge height while keeping a higher SEA value, and has excellent bulletproof performance.
Fig. 2 and 3 are an apparent topography and internal CT scan results of the composite target after the backfire experiment in example 2. According to the figure, after the bullet penetrates through the bullet-facing surface PI fiber layer, the UHMWPE fiber reinforced core layer is continuously penetrated, a large amount of layering phenomena occur in the area of the target plate core layer, and the bullet can only penetrate through the core layer with partial thickness and finally stays in the target plate core layer. In addition, the interface between the PI fiber layer on the back elastic surface of the target plate and the UHMWPE layer is also subjected to interface delamination caused by stress wave reflection. The hybrid structure can fully exert the advantage of small back bulge of the PI fibers in the bouncing process, fully exert the advantage of high energy absorption of the UHMWPE fibers of the core layer, and avoid the problem of large back bulge caused by placing the UHMWPE fibers on the back bouncing surface of the composite material, so that the hybrid structure is an ideal hybrid structure. The introduction of the interface reinforcing layer can ensure the integrity of the composite material in the protection process, avoid splitting caused by large-area layering, further limit the deformation of the back of the composite material and achieve the effect of reducing the back convexity.
Figure 4 is a plot of the backface signature of the composite target after backface firing test in comparative example 2, which shows a large area of rhomboid deformation centered on the impact point compared to the ballistic composite of the invention.
The foregoing describes preferred embodiments of the present invention, but is not intended to limit the invention thereto. Modifications and variations of the embodiments disclosed herein may be made by those skilled in the art without departing from the scope and spirit of the invention.
Claims (10)
1. A polyimide fiber/ultra-high molecular weight polyethylene fiber bulletproof composite material has the following structure:
include the infrastructure in proper order, meet bullet layer, interface layer, intermediate level, interface layer, the layer of playing on the back, its characterized in that:
the reinforced fibers of the bullet facing layer and the bullet backing layer are high-strength high-modulus polyimide fibers;
the reinforced fiber of the middle layer is ultra-high molecular weight polyethylene fiber, and the total thickness of the bullet facing layer and the bullet backing layer is 0.2-1 compared with the thickness of the middle layer by taking the thickness of the middle layer as a reference;
the missile-facing layer, the middle layer and the missile-backing layer are all made by unidirectional arrangement in a fiber surface and orthogonal laying between layers, and the interface layer is an interface formed by the surface layers of two types of fibers and a thermoplastic resin film introduced for enhancing the bonding strength of the interface at the junction;
the bulletproof composite material is characterized in that the composition of the bullet facing layer and the composition of the bullet backing layer are the same, the bulletproof composite material is a resin matrix composite material taking high-strength and high-modulus polyimide fibers as a reinforcement, and the middle layer is a resin matrix composite material taking ultra-high molecular weight polyethylene fibers as a reinforcement.
2. The ballistic resistant composite material of claim 1 wherein the thickness ratio of the ballistic facing layer to the ballistic backing layer is 1: 0.9-1.
3. Ballistic resistant composite material according to claim 1, characterized in that the matrix of the resin based composite material is one or more thermoplastic resins of polyurethane resins, polyvinyl butyral based resins, styrene butadiene block copolymers, polycarbonate resins.
4. The bulletproof composite material as claimed in claim 1, wherein the resin-based composite material of the bullet-facing layer and the bullet-back layer comprises 70-90% of high-strength high-modulus polyimide fibers and 10-30% of resin matrix.
5. Ballistic resistant composite material according to claim 1, characterized in that the resin-based composite material of the intermediate layer comprises 70-90% by mass of ultra-high molecular weight polyethylene fibres and 10-30% by mass of resin matrix.
6. Ballistic resistant composite material according to claim 1, characterized in that the high strength and high modulus polyimide fibers have a tensile strength of not less than 3.4GPa and a tensile modulus of not less than 110 GPa.
7. Ballistic resistant composite material according to claim 1, characterized in that the ultra high molecular weight polyethylene fibres have a tensile strength of not less than 3.2GPa and a tensile modulus of not less than 100 GPa.
8. A preparation method of a polyimide fiber/ultra-high molecular weight polyethylene fiber bulletproof composite material is characterized by comprising the following steps:
(1) sequentially spreading prepregs which are respectively unidirectionally arranged by high-orientation polyimide fibers/ultrahigh molecular weight polyethylene fibers according to a fiber arrangement direction of 0 DEG/90 DEG, and paving a layer of thermoplastic resin film at the interface between the bullet facing layer and the intermediate layer and the interface between the intermediate layer and the back bullet layer to reinforce the interface;
(2) and (3) placing the laid prepreg into a mould, and carrying out hot-press molding at the hot-press temperature of 70-130 ℃ under the pressure of 0.5-5 MPa for 0.1-1 hour.
9. Ballistic resistant composite material according to claim 8, characterized in that the thermoplastic resin is one or more of a polyurethane resin, a polyvinyl butyral based resin, a styrene butadiene block copolymer, a polycarbonate resin.
10. The ballistic resistant composite material according to claim 8 wherein the interface is reinforced by a specific process comprising: the thickness of the thermoplastic resin film is controlled to be within 0.1mm, and the area density is controlled to be 100g/m 2 The area of the resin film is consistent with the area of the laying layer of the prepreg, and the hot-press molding temperature of the film is controlled within a hot-press temperature interval; the thermoplastic resin film is in the form of one or more of a glue film, a net film or a grid glue film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210563235.6A CN114957989B (en) | 2022-05-19 | 2022-05-19 | Bulletproof composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210563235.6A CN114957989B (en) | 2022-05-19 | 2022-05-19 | Bulletproof composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114957989A true CN114957989A (en) | 2022-08-30 |
| CN114957989B CN114957989B (en) | 2024-02-27 |
Family
ID=82985990
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210563235.6A Active CN114957989B (en) | 2022-05-19 | 2022-05-19 | Bulletproof composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114957989B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070238379A1 (en) * | 2006-03-30 | 2007-10-11 | Honeywell International Inc. | Molded ballistic panel with enhanced structural performance |
| US8080486B1 (en) * | 2010-07-28 | 2011-12-20 | Honeywell International Inc. | Ballistic shield composites with enhanced fragment resistance |
| CN105064038A (en) * | 2015-08-24 | 2015-11-18 | 江苏先诺新材料科技有限公司 | Method for preparing water-soluble polyimide sizing agent for polyimide fiber and application thereof |
| CN107793700A (en) * | 2016-09-02 | 2018-03-13 | 江苏先诺新材料科技有限公司 | The composite of a kind of carbon fiber/polyamide imine fiber hybrid fabric as enhancing main body and preparation method thereof |
| CN111267429A (en) * | 2020-03-13 | 2020-06-12 | 南通大学 | UHMWPE fiber reinforced resin-based soft bulletproof material |
-
2022
- 2022-05-19 CN CN202210563235.6A patent/CN114957989B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070238379A1 (en) * | 2006-03-30 | 2007-10-11 | Honeywell International Inc. | Molded ballistic panel with enhanced structural performance |
| US8080486B1 (en) * | 2010-07-28 | 2011-12-20 | Honeywell International Inc. | Ballistic shield composites with enhanced fragment resistance |
| CN105064038A (en) * | 2015-08-24 | 2015-11-18 | 江苏先诺新材料科技有限公司 | Method for preparing water-soluble polyimide sizing agent for polyimide fiber and application thereof |
| CN107793700A (en) * | 2016-09-02 | 2018-03-13 | 江苏先诺新材料科技有限公司 | The composite of a kind of carbon fiber/polyamide imine fiber hybrid fabric as enhancing main body and preparation method thereof |
| CN111267429A (en) * | 2020-03-13 | 2020-06-12 | 南通大学 | UHMWPE fiber reinforced resin-based soft bulletproof material |
Non-Patent Citations (1)
| Title |
|---|
| 沈莉莉;: "先诺新材建成世界首套年产30t规模的高强高模聚酰亚胺纤维生产装置", 合成纤维, no. 04, pages 54 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114957989B (en) | 2024-02-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI359935B (en) | Frag shield | |
| US8887312B2 (en) | Helmets comprising ceramic for protection against high energy fragments and rifle bullets | |
| EP0197279B1 (en) | Complex composite article having improved impact resistance | |
| US20120186433A1 (en) | Protective shield material | |
| EP3294542B1 (en) | Ballistic and stab resistant composite | |
| KR20160048768A (en) | Ballistic resistant sheets, articles comprising such sheets and methods of making the same | |
| US20070293109A1 (en) | Composite material for stab, ice pick and armor applications | |
| CN107059404B (en) | A kind of resistance to deformation material and its preparation method and application | |
| KR20090115959A (en) | Protective helmets | |
| KR20120113764A (en) | Enhanced lightweight ballistic materials | |
| CN104669725B (en) | A kind of assorted fibre multidimensional bulletproof composite breast plate and preparation method thereof | |
| CN110103556A (en) | A kind of flexible ballistic-resistant stab-resistant material and preparation method thereof | |
| CA2391505C (en) | Protective material | |
| JP2011503494A (en) | Polyolefin fiber reinforced rubber | |
| CN103600536A (en) | Composite material for bulletproof helmet and preparation method thereof | |
| TW202031473A (en) | Ballistic-resistant molded article | |
| KR102134696B1 (en) | Hybrid armor with carbon nanotube sheet | |
| KR20150003471A (en) | Bulletproof Composite Material and Bulletproof Helmet Manufactured therewith | |
| CN114957989B (en) | Bulletproof composite material and preparation method thereof | |
| CN208887480U (en) | Basalt bullet proof composite plating | |
| CN111703088B (en) | Preparation method of fragment convergence type bulletproof composite material | |
| CN211926644U (en) | Ultralight bullet-resistant composite board suitable for manufacturing light combat tank | |
| CN114932735B (en) | Bulletproof composite material designed according to modulus matching and preparation method thereof | |
| US20110283875A1 (en) | Textile structure resistant to the impact of bullets and to the penetration of sharp and/or pointed elements and relative production method | |
| KR101595729B1 (en) | Bullet-proof material and method for manufacturing the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |