CN114932735A - Bulletproof composite material designed according to modulus matching and preparation method thereof - Google Patents
Bulletproof composite material designed according to modulus matching and preparation method thereof Download PDFInfo
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- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/42—Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/06—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the heating method
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/10—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the pressing technique, e.g. using action of vacuum or fluid pressure
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- 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
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- 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
-
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
- B32B2260/02—Composition of the impregnated, bonded or embedded layer
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/558—Impact strength, toughness
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
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- B32B2571/00—Protective equipment
- B32B2571/02—Protective equipment defensive, e.g. armour plates or anti-ballistic clothing
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- Engineering & Computer Science (AREA)
- General Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Ceramic Engineering (AREA)
- Laminated Bodies (AREA)
- Aiming, Guidance, Guns With A Light Source, Armor, Camouflage, And Targets (AREA)
- Reinforced Plastic Materials (AREA)
Abstract
The invention provides a bulletproof composite material designed according to modulus matching and a preparation method thereof. The bulletproof composite material comprises a thermoplastic resin matrix composite material which is laid on the bullet-facing surface and takes high-strength and high-modulus fibers as reinforcements, and a thermoplastic resin matrix composite material which is laid on the bullet-facing surface and takes high-strength and high-toughness fibers as reinforcements. According to the invention, the high-strength high-modulus Polyimide (PI) fiber is laid on the bullet-facing surface, the high-strength high-toughness PI fiber is laid on the bullet-back surface, and the high-strength high-toughness PI fiber and the bullet-back surface are combined through hot pressing to prepare the laminated board, so that the advantages of high stress wave transmission rate of the high-strength high-modulus PI fiber and high bullet-proof effect of the high-strength high-toughness PI fiber are fully exerted.
Description
Technical Field
The invention relates to a bulletproof composite material designed according to modulus matching and a preparation method thereof, belonging to the field of bulletproof composite materials.
Background
The bulletproof composite materials used by the prior bulletproof helmets and bulletproof clothes mainly comprise high-performance fiber reinforced resin matrix composite materials. The fiber reinforcement mainly comprises aramid fiber, ultra-high molecular weight polyethylene fiber and the like. The bulletproof composite material is mainly composed of a reinforced fiber and a resin matrix, such as an aramid fiber reinforced polyurethane resin bulletproof composite material, so that the mechanical properties of all layers in the composite material are completely the same.
Research shows that [ Kongchunfeng, Tianwei, Wengpu-luck, congling peak, congratulations ] impact resistance research of high-performance fiber laminated composite [ J ]. student of Zhejiang university of science (Nature science edition), 2016,35(03): 367-. Therefore, there are studies on the use of two or more types of fibers in the preparation of bulletproof composites through ply combination design [ Sunjie, Zhao Juan, application of fiber-reinforced bulletproof composites and current research situation [ J ] chemical fiber and textile technology, 2021,50(01):7-11+53], but it only uses the characteristics of different types of fibers in terms of mechanical strength, such as high specific strength and high specific toughness of ultra-high molecular weight polyethylene fibers, high strength of para-aramid fibers, and the like, and only uses deformation, breakage, debonding of fibers to absorb energy.
The ballistic effectiveness is determined by both energy absorption and energy diffusion propagation, but the prior art does not fully consider another factor in material design that affects ballistic effectiveness, namely the rate of transmission of stress waves. The prior art does not carry out combined design according to the impact action and the stress wave transmission characteristic of a penetration body.
Disclosure of Invention
The invention aims to provide a bulletproof composite material and a preparation method thereof.
The bulletproof composite material provided by the invention comprises a thermoplastic resin matrix composite material which is laid on a bullet-facing surface and takes high-strength and high-modulus fibers as reinforcements, and a thermoplastic resin matrix composite material which is laid on a back bullet surface and takes high-strength and high-toughness fibers as reinforcements.
The tensile strength of the high-strength high-modulus fiber is more than or equal to 2.5GPa, the modulus is more than or equal to 130GPa, and the stress wave transmission rate C calculated according to the formula (1) is more than or equal to 9500 m/s;
the tensile strength of the high-strength high-toughness fibers is more than or equal to 3.0GPa, and the bulletproof efficacy parameter calculated according to the formula (2)
The formula (1) is a stress wave transmission rate formula; the formula (2) is a bulletproof efficacy formula. Wherein σ is the fiber tensile strength, ε is the fiber elongation at break, ρ is the fiber density, and E is the fiber modulus.
The high-strength high-modulus fiber can be one or a mixture of several of PI fiber, PBO fiber, carbon fiber and ultra-high molecular weight polyethylene fiber, preferably PI fiber (the tensile strength is more than or equal to 2.5GPa, the modulus is more than or equal to 130GPa, and the stress wave transmission rate C calculated according to the formula (1) is more than or equal to 9500m/S), and more preferably PI fiber with the specification of S30M and above;
the high-strength high-toughness fibers can be one or a mixture of more of PI fibers, PBO fibers, carbon fibers and ultrahigh molecular weight polyethylene fibers, and preferably are PI fibers (the tensile strength is more than or equal to 3.0GPa, and the bulletproof efficacy calculated according to the formula (2)Number of
More preferably PI fiber with the specification of S35 and above;
the reinforcement structure is unidirectional cloth (UD cloth) or fabric;
the thermoplastic resin is polyurethane and/or polyvinyl butyral and modified resin thereof.
The invention also provides a method for preparing the bulletproof composite material.
The method for preparing the bulletproof composite material comprises the following steps:
1) respectively preparing a thermoplastic resin matrix composite material taking high-strength and high-modulus fibers as reinforcements and a thermoplastic resin matrix composite material taking high-strength and high-toughness fibers as reinforcements;
2) laminating the laminated plates: laying a plurality of layers of thermoplastic resin matrix composite materials taking high-strength and high-modulus fibers as reinforcements together to serve as a bullet-facing surface, laying a plurality of layers of thermoplastic resin matrix composite materials taking high-strength and high-toughness fibers as reinforcements together to serve as a bullet-backing surface, and forming a laminated board;
3) placing the obtained laminated plate in a mould, and carrying out hot press molding to obtain the laminated plate;
in the step 1) of the method, the structure of the reinforcing body is fiber UD cloth, and the areal density of the fiber UD cloth is about 100g/m 2 ；
In the step 2), designing a [0 °/90 ° ] orthogonal layering structure according to the modulus matching design requirement;
in the step 3) of the method, the hot-press molding temperature can be 150 ℃ and preferably 135 ℃ and more preferably 128 ℃, the hot-press molding pressure can be 0.5-5MPa, preferably 0.5-2MPa and more preferably 1MPa, and the holding time can be 5-50min, preferably 20-40min and more preferably 30 min.
The tensile deformation and the breakage of the fiber are the main energy absorption modes of the composite material bulletproof target plate, and the size of the energy absorption modes depends on two aspects: one is the ability of the fiber to absorb energy. The energy absorption capability of different fibers can be compared by the empirical formula of Cunnif energy absorption [ MIAO M. dynamic modules and string wave in fibrous fibers [ J ]. Journal of Materials Science,2016,51(12):5939-47], and generally, the greater the tensile strength of the fiber, the higher the elongation at break, the better the energy absorption effect. Ballistic resistant composites therefore require the use of high performance fibers. The second is the number of fibers that participate in energy absorption. The bullet contacts the target plate, the fiber yarn directly contacting the bullet is the main yarn, and the other yarns are the secondary yarns. The main yarn can directly absorb energy but has a small proportion, the secondary yarn has a large proportion, and the secondary yarn can participate in energy absorption only by stress wave transmission. The rate of stress wave transmission depends on the density and modulus of the fibre, the smaller the density, the greater the modulus, the faster the stress wave transmission. The invention considers the stress wave transmission and fiber energy absorption capacity at the same time, uses the high-strength high-toughness fiber to absorb energy, uses the high-strength high-modulus fiber to transmit the stress wave, and the two are well matched, so that the composite material can fully exert the bulletproof capacity.
The prior art has been much studied with respect to the absorption of energy. The invention mainly solves the problem that the energy spreading and diffusion are not fully considered in the design of the composite material in the prior art, and the faster the energy spreading is, the more yarns can participate in the energy absorption on the surface of the target plate, so that the composite material designed in the way has higher specific absorption energy.
According to the invention, the high-strength high-modulus PI fiber is laid on the bullet-facing surface, the high-strength high-toughness PI fiber is laid on the bullet-back surface, and the high-strength high-toughness PI fiber and the bullet-back surface are combined through hot pressing to prepare the laminated board, so that the advantages of high stress wave transmission rate of the high-strength high-modulus PI fiber and high bulletproof efficacy of the high-strength high-toughness PI fiber are fully exerted.
Drawings
FIG. 1 is a schematic view showing the structure of the mat layer of the target boards I, II, III and IV in example 1 of the present invention.
Fig. 2 is a slice view of the target plate in the thickness direction of the micro-nano focus CT scanning, and the arrow direction is the bullet shooting direction, wherein in a1, a2 and a3, a4, high-strength and high-modulus PI fibers are used as bullet-facing surfaces, and in b1, b2, b3 and b4, high-strength and high-toughness PI fibers are used as bullet-facing surfaces.
Fig. 3 is a target plate bullet-facing surface micro-nano focus CT scanning pore distribution diagram. (a) In (b) high-strength high-toughness PI fiber is used as bullet-facing surface
Detailed Description
The preferred embodiments of the present invention will be described in conjunction with the accompanying drawings, and it will be understood that they are described herein for the purpose of illustration and explanation and not limitation.
Example 1
In this example, the high-strength high-modulus PI fiber is S30M type (tensile strength 3.1GPa, modulus 164GPa, elongation at break 2.1%, density 1.44 g/cm) 3 The wave velocity C of the stress wave calculated by the formula (1) is 10691m/S), and the high-strength high-toughness PI fiber is S35 type (tensile strength is 3.5GPa, modulus is 123GPa, breaking elongation is 3.2 percent, and density is 1.44g/cm 3 The bulletproof efficacy is calculated by the formula (2)
Is 712 m/s).
The preparation method of the composite material bulletproof target plate containing the modulus matching design comprises the following steps:
a. preparing fiber UD cloth
The S30M type fiber/S35 type fiber impregnated with polyurethane was uniformly arranged in parallel on a support film by using a winder to prepare S30M type fiber UD cloth/S35 type fiber UD cloth with an areal density of about 100g/m 2 ；
b. Cutting sample
Cutting the UD cloth prepared in the previous step into sample pieces of 300 multiplied by 300 mm;
c. laminate ply
The [0 °/90 ° ] orthogonal ply structure design is required according to the modulus matching design (i.e., the angle between each ply and each layer is 90 °), as shown in fig. 1. No. I: laying 60 layers of S35 type fiber UD cloth; II: laying 60 layers of S30M type fiber UD cloth; no. iii and IV: 12 layers of S30M type fiber UD cloth and 48 layers of S35 type fiber UD cloth, wherein the UD cloth side of the S30M type fiber is used as a bullet-facing surface for the No. III sample, and the UD cloth side of the S35 type fiber is used as a bullet-facing surface for the No. IV sample.
d. Hot pressing of laminated board
Respectively placing the laminated plates I, II, III and IV in a mould, hot-pressing in a hot press at 128 ℃ under 1MPa for 30 min.
TABLE 1 test results of targeting tests on the target boards prepared in EXAMPLE 1
As can be seen from the data in table 1: the bulletproof performance of the No. I target plate is superior to that of the No. II target plate. This is because the tensile strength and elongation at break of the S35 type fiber are higher than those of the S30M fiber, and the ballistic effectiveness of the S35 fiber is higher than that of the S30M fiber according to the experimental formula of Cunniff ballistic effectiveness. After the modulus matching design, the bulletproof efficacy of the III target board is higher than that of the I target board, because the high-strength high-modulus PI fiber of the S30M type is laid on the bullet-facing surface of the III target board, when a bullet contacts the target board, the transmission speed of stress waves is high, the energy is rapidly diffused in the plane range of the target board, and the quantity of secondary yarns participating in energy absorption is increased. Meanwhile, the high-strength and high-toughness S35 type PI fibers on the back elastic surface can play a good energy absorption role, so that the V50 value and the SEA value are obviously improved compared with a pure S35 fiber target plate and a pure S30M fiber target plate. However, when the bullet-facing surface adopts the S35 type fiber and the bullet-backing surface adopts the S30M type fiber (sample plate No. IV), the bulletproof effect is significantly reduced, and is only slightly higher than that of a pure S30M type fiber target plate (sample plate No. ii), and both fibers do not sufficiently exert their respective effects.
FIG. 2 is a micro-nano focus CT scanning slice image in the thickness direction of the target plate. The preparation method of the target plate is the same as that of example 1, wherein a1, a2, a3 and a4 are high-strength high-modulus fiber projectile-oriented materials, and the specific preparation method refers to the No. III target plate in example 1; b1, b2, b3 and b4 are high-strength high-tenacity fibers, and the specific preparation method refers to the target plate No. IV in example 1.
As can be seen from fig. 2, when the high-strength high-model PI fiber is on the bullet-facing surface, the target plate is spread in a fan shape, and a large number of layers are shown; when the high-strength and high-toughness PI fiber is on the bullet-facing surface, the target plate is in a rhombic layered state, the layered area is obviously reduced, and the energy absorption effect is also reduced. More noteworthy, when the bullet-facing surface is high-strength high-modulus PI fiber, a great deal of deformation and breakage phenomena occur on the fiber on the bullet-facing surface side, which indicates that enough fiber participates in energy absorption, so that the bulletproof efficacy is higher.
Fig. 3 is a micro-nano focus CT scanning aperture distribution diagram of the bullet-facing surface of the target plate. The preparation method of the target plate is the same as that of example 1, wherein (a) is high-strength high-modulus fiber ballistic-resistant, and the specific preparation method refers to the No. III target plate in example 1; (b) for high-strength high-toughness fiber ballistic resistance, the specific preparation method refers to the No. IV target plate in example 1
As can be seen from fig. 3, when the high-strength high-modulus PI fiber is on the bullet-facing surface, the target plate is layered and radially diffused to the periphery with the impact point as the center; when the high-strength high-toughness PI fiber is on the bullet-facing surface, the target plate takes the bullet point as the center, and the cross-shaped layered appearance is presented along the main yarn fiber direction. The former has a larger damage area when penetrated by a bullet, indicating that more fibers and resins are involved in energy absorption.
Through V50 test, micro-nano focus CT scanning, all proved the modulus matching design scheme that this scheme provided: the high-strength high-modulus PI fiber is laid on one side of the bullet-facing surface, and the high-strength high-toughness PI fiber is laid on one side of the bullet-backing surface, so that the performance advantages of the high-strength high-modulus PI fiber and the high-toughness PI fiber can be fully exerted, namely the high-strength high-modulus PI fiber is beneficial to energy transmission, and the high-strength high-toughness PI fiber is beneficial to energy absorption. Compared with other paving layer structure designs, the good matching of the two has a higher SEA value.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (9)
1. A bulletproof composite material comprises a thermoplastic resin matrix composite material which is laid on a bullet-facing surface and takes high-strength and high-modulus fibers as reinforcements, and a thermoplastic resin matrix composite material which is laid on a bullet-back surface and takes high-strength and high-toughness fibers as reinforcements.
2. Ballistic resistant composite material according to claim 1, characterized in that: the tensile strength of the high-strength high-modulus fiber is more than or equal to 2.5GPa, the modulus is more than or equal to 130GPa, and the stress wave transmission rate C calculated according to the formula (1) is more than or equal to 9500 m/s;
the tensile strength of the high-strength high-toughness fibers is more than or equal to 3.0GPa, and the bulletproof efficacy parameter calculated according to the formula (2)
The formula (1) is a stress wave transmission rate formula; formula (2) is a bulletproof efficacy formula; wherein σ is the fiber tensile strength, ε is the fiber elongation at break, ρ is the fiber density, and E is the fiber modulus.
3. Ballistic resistant composite material according to claim 1 or 2, characterized in that: the high-strength high-modulus fiber is one or a mixture of more of Polyimide (PI) fiber, poly (p-Phenylene Benzobisoxazole) (PBO) fiber, carbon fiber, aramid fiber and ultrahigh molecular weight polyethylene fiber;
the high-strength high-toughness fibers are one or a mixture of more of PI fibers, PBO fibers, carbon fibers, aramid fibers and ultrahigh molecular weight polyethylene fibers;
the reinforcement structure is a Unidirectional (UD) cloth or fabric;
the thermoplastic resin is polyurethane and/or polyvinyl butyral and modified resin thereof.
4. A ballistic resistant composite material according to claim 3, characterized in that: the high-strength high-modulus fiber is a high-strength high-modulus PI fiber, the tensile strength is more than or equal to 2.5GPa, the modulus is more than or equal to 130GPa, and the stress wave transmission rate C calculated according to the formula (1) is more than or equal to 9500 m/s;
the high-strength high-toughness fibers are high-strength high-toughness PI fibers, the tensile strength is more than or equal to 3.0GPa, and the bulletproof efficacy parameters are calculated according to the formula (2)
5. A process for the preparation of a ballistic resistant composite material according to any one of claims 1 to 4 comprising the steps of:
1) respectively preparing a thermoplastic resin matrix composite material taking high-strength and high-modulus fibers as reinforcements and a thermoplastic resin matrix composite material taking high-strength and high-toughness fibers as reinforcements;
2) laminating the laminated plates: laying a plurality of layers of thermoplastic resin matrix composite materials taking high-strength and high-modulus fibers as reinforcements together to serve as a bullet-facing surface, laying a plurality of layers of thermoplastic resin matrix composite materials taking high-strength and high-toughness fibers as reinforcements together to serve as a bullet-facing surface, and forming a laminated board;
3) and placing the obtained laminated plate in a mould, and carrying out hot press molding to obtain the laminated plate.
6. The method of claim 5, wherein: in the step 1), the structure of the reinforcement body is fiber UD cloth, and the areal density of the fiber UD cloth is about 100g/m 2 。
7. The method according to claim 5 or 6, characterized in that: in the step 2), the structure is designed in a [0 °/90 ° ] orthogonal layering structure.
8. The method according to any one of claims 5-7, wherein: in the step 3), the hot-press molding temperature is 100-150 ℃, the hot-press molding pressure is 0.5-5MPa, and the heat preservation time is 5-50 min.
9. Use of the ballistic resistant composite material according to any one of claims 1 to 4 for the production of helmets, body armor, ballistic panels.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115847965A (en) * | 2022-10-24 | 2023-03-28 | 东莞市雄林新材料科技股份有限公司 | Bulletproof film for automobile |
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