A gradient bulletproof and impact-resistant composite material

Abstract

This invention provides a gradient ballistic and impact-resistant composite material, comprising, in sequence, a first composite material layer, a second composite material layer, and a third composite material layer; wherein the modulus of the first, second, and third composite material layers decreases sequentially; the modulus includes flexural modulus and storage modulus. This gradient composite material, with its modulus (elastic modulus and storage modulus) decreasing sequentially from front to back and its flexibility gradually increasing, conforms to the mechanical response law under high-speed impact loads. It can fully utilize the characteristics of each material layer, effectively improving the ultimate V50, and has broad application value in the field of armor protection.

Description

Technical Field

[0001] This invention relates to the field of armor protection, and in particular to a gradient ballistic and impact-resistant composite material. Background Art

[0002] In recent decades, armor protection materials have been continuously developing towards high performance and lightweight, from armor steel and aluminum alloys to lightweight bulletproof materials such as bulletproof ceramics and fiber-reinforced resin-based composites, with the protective effectiveness per unit weight gradually improving. Organic high-performance fibers such as aramid, PBO fiber, polyimide fiber, and ultra-high molecular weight polyethylene fiber have advantages such as low density, high strength, and high toughness, and have been widely used in bulletproof composite materials.

[0003] The mechanical response of composite materials under high-speed impact loads such as bullets and fragments differs significantly from that under quasi-static loading. In the initial stage of the impact, shear plugging failure primarily occurs at the impact center (the front end of the composite material). As the impact progresses, tensile waves formed by the reflection of the compressive wave cause tensile failure primarily at the rear end of the composite material. Therefore, the primary damage mode of ballistic composite materials changes from front to back under high-speed impact loads. This necessitates that each layer of the composite material possess different performance characteristics to match the failure modes at each stage of high-speed impact, thus posing a significant challenge to material development. Summary of the Invention

[0004] In view of this, the present invention provides a gradient ballistic and impact-resistant composite material. The gradient ballistic and impact-resistant composite material provided by the present invention can effectively improve the protective effect.

[0005] This invention provides a gradient bulletproof and impact-resistant composite material, comprising, in sequence, a first composite material layer, a second composite material layer, and a third composite material layer;

[0006] The modulus of the first composite material layer, the second composite material layer, and the third composite material layer decreases sequentially; the modulus includes flexural modulus and storage modulus.

[0007] The first composite material layer is made of organic fiber and epoxy resin; the modulus of the first composite material layer at 20°C is as follows: flexural modulus ≥32GPa, storage modulus ≥24GPa;

[0008] The second composite material layer is made of organic fibers and epoxy resin-based resin; the modulus of the second composite material layer at 20°C is as follows: flexural modulus 10-32 GPa, storage modulus 5-24 GPa;

[0009] The third composite material layer is made of organic fiber and epoxy resin modified polyvinyl butyral resin; the modulus of the third composite material layer at 20°C is as follows: flexural modulus 2-10 GPa, storage modulus 0.5-5 GPa.

[0010] Preferably, in the first composite material layer:

[0011] The epoxy resin-based resin is prepared by the following method: mixing epoxy resin, curing agent and accelerator and heating to obtain epoxy resin-based resin;

[0012] in:

[0013] The epoxy resin is at least one of bisphenol A epoxy resins E-20, E-35, E-44, E-51 and multifunctional epoxy resin AG-80;

[0014] The curing agent is dicyandiamide;

[0015] The accelerator is an organic urea accelerator;

[0016] The proportions of the above raw materials by weight are as follows: epoxy resin 80-88 parts, curing agent 8-10 parts, accelerator 2-5 parts;

[0017] The heating temperature is 50–70°C;

[0018] In the second composite material layer:

[0019] The epoxy resin-based resin is prepared by the following method: mixing epoxy resin, curing agent and accelerator and heating to obtain epoxy resin-based resin;

[0020] in:

[0021] The epoxy resin is at least one of bisphenol A epoxy resins E-20, E-35, E-44, E-51 and multifunctional epoxy resin AG-80;

[0022] The curing agent is dicyandiamide;

[0023] The accelerator is an organic urea accelerator;

[0024] The proportions of the above raw materials by weight are as follows: epoxy resin 80-88 parts, curing agent 8-10 parts, accelerator 2-5 parts;

[0025] The heating temperature is 50–70°C.

[0026] Preferably, in the third composite material layer:

[0027] The epoxy resin modified polyvinyl butyral resin is prepared by the following method: epoxy resin, curing agent, polyvinyl butyral and diluent are mixed and dissolved, and then the diluent is removed by heating to obtain epoxy resin modified polyvinyl butyral resin.

[0028] in:

[0029] The epoxy resin is at least one of bisphenol A epoxy resins E-20, E-35, E-44, E-51 and multifunctional epoxy resin AG-80;

[0030] The curing agent is dicyandiamide;

[0031] The weight-average molecular weight of the polyvinyl butyral is 80,000 to 110,000.

[0032] The diluent is a mixture of ethanol and isopropanol;

[0033] The proportions of the above raw materials by weight are as follows: epoxy resin 5-30 parts, curing agent 1-3 parts, polyvinyl butyral 70-90 parts, and diluent 150 parts.

[0034] Preferably, in the first composite material layer, the organic fiber is a high-modulus grade fiber among aramid III fiber, PBO fiber, or polyimide fiber, and the elastic modulus of the high-modulus grade fiber is 140-280 GPa.

[0035] In the second composite material layer, the organic fiber is a medium modulus grade fiber among aramid III fiber, PBO fiber, or polyimide fiber; the elastic modulus of the medium modulus grade fiber is 80-180 GPa, and the elastic modulus is lower than that of the organic fiber in the first composite material layer.

[0036] In the third composite material layer, the organic fiber is a medium modulus grade fiber among aramid III fiber, PBO fiber, or polyimide fiber; the elastic modulus of the medium modulus grade fiber is 80-180 GPa, and the elastic modulus is lower than that of the organic fiber in the first composite material layer.

[0037] Preferably, in the first composite material layer, the organic fiber is aramid STARAMID F-358 or PBO-HM;

[0038] In the second composite material layer, the organic fiber is at least one of aramid STARAMID F-368, PBO-AS, polyimide fiber S30, and polyimide fiber S35;

[0039] In the third composite material layer, the organic fiber is at least one of aramid STARAMID F-368, PBO-AS, polyimide fiber S30, and polyimide fiber S35.

[0040] Preferably, the first composite material layer is prepared by the following method: mixing epoxy resin-based resin and organic fiber, and heating and curing to obtain the first composite material;

[0041] in:

[0042] The preferred mass ratio of epoxy resin-based resin to organic fiber is (43-54):100;

[0043] The conditions for heat curing are: temperature 120-130℃, pressure 0.3-1.0MPa, and time 1-3h.

[0044] Preferably, the second composite material layer is prepared by mixing epoxy resin-based resin and organic fiber, and then heating and curing to obtain the second composite material;

[0045] in:

[0046] The mass ratio of the epoxy resin-based resin to the organic fiber is (25-43):100;

[0047] The conditions for heat curing are: temperature 120-130℃, pressure 0.3-1.0MPa, and time 1-3h.

[0048] Preferably, the third composite material layer is prepared by the following method: mixing epoxy resin-modified polyvinyl butyral resin and organic fibers, and then heating and curing to obtain the third composite material;

[0049] in:

[0050] The mass ratio of the epoxy resin-modified polyvinyl butyral resin to the organic fiber is (14-25):100.

[0051] The conditions for heat curing are: temperature 150-165℃, pressure 0.5-1.0MPa, and time 10-60min.

[0052] Preferably, the thickness of the first composite material layer is 2–8 mm;

[0053] The thickness of the second composite material layer is 2–8 mm;

[0054] The thickness of the third composite material layer is 2 to 5 mm.

[0055] Preferably, the gradient bulletproof and impact-resistant composite material is prepared by the following method:

[0056] A composite board is formed by hot-melt adhesive film bonding between the first composite material layer, the second composite material layer and the third composite material layer, and hot-pressing the composite material together.

[0057] The conditions for hot-press composite molding are: temperature 90-120℃, pressure 0.6-1.0MPa, and time 1-3h.

[0058] This invention provides a gradient bulletproof and impact-resistant composite material, comprising, in sequence, a first composite material layer, a second composite material layer, and a third composite material layer; wherein the modulus of the first, second, and third composite material layers decreases sequentially; the modulus includes flexural modulus and storage modulus; the first composite material layer is made of organic fibers and epoxy resin-based resin; the modulus of the first composite material layer at 20°C is as follows: flexural modulus ≥ 32 GPa, storage modulus ≥ 24 GPa; the second composite material layer is made of organic fibers and epoxy resin-based resin; the modulus of the second composite material layer at 20°C is as follows: flexural modulus 10–32 GPa, storage modulus 5–24 GPa; the third composite material layer is made of organic fibers and epoxy resin-modified polyvinyl butyral resin; the modulus of the third composite material layer at 20°C is as follows: flexural modulus 2–10 GPa, storage modulus 0.5–5 GPa. The aforementioned gradient composite material exhibits a decreasing modulus (elastic modulus and storage modulus) and a gradually increasing flexibility from front to back, conforming to the mechanical response law under high-speed impact loads. It can fully utilize the characteristics of each layer of material, effectively improve the ultimate V50, and has broad application value in the field of armor protection. Detailed Implementation

[0059] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application.

[0060] In this article, the technical features described in an open-ended manner include both closed technical solutions composed of the listed features and open technical solutions that include the listed features.

[0061] The term “and / or” as used herein includes any and all combinations of one or more of the related listed items.

[0062] In this document, numerical ranges are referred to as continuous unless otherwise specified, and include the minimum and maximum values ​​of the range, as well as every value between the minimum and maximum values. Furthermore, when a range refers to an integer, it includes every integer between the minimum and maximum values ​​of the range. Additionally, when multiple ranges are provided to describe a feature or characteristic, the ranges may be combined. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges to which they are incorporated.

[0063] A gradient bulletproof and impact-resistant composite material, comprising, in sequence, a first composite material layer, a second composite material layer, and a third composite material layer;

[0064] The modulus of the first composite material layer, the second composite material layer, and the third composite material layer decreases sequentially; the modulus includes flexural modulus and storage modulus.

[0065] The first composite material layer is made of organic fiber and epoxy resin; the modulus of the first composite material layer at 20°C is as follows: flexural modulus ≥32GPa, storage modulus ≥24GPa;

[0066] The second composite material layer is made of organic fibers and epoxy resin-based resin; the modulus of the second composite material layer at 20°C is as follows: flexural modulus 10-32 GPa, storage modulus 5-24 GPa;

[0067] The third composite material layer is made of organic fiber and epoxy resin modified polyvinyl butyral resin; the modulus of the third composite material layer at 20°C is as follows: flexural modulus 2-10 GPa, storage modulus 0.5-5 GPa.

[0068] Based on the mechanical response law of composite materials under high-speed impact load, this invention designs a gradient bulletproof and impact-resistant composite material. The front end adopts a high modulus design, the middle layer transitions, and the rear end adopts a high flexibility design, giving full play to the characteristics of each layer of material to achieve a better protective effect.

[0069] [Regarding the first composite material layer]:

[0070] In this invention, the first composite material layer is made of organic fibers and epoxy resin-based resin.

[0071] In this invention, the organic fiber used is a high-modulus organic fiber, preferably a high-modulus grade fiber among aramid III fiber, PBO fiber or polyimide fiber, wherein the elastic modulus of the high-modulus grade fiber is 140 to 280 GPa; specifically preferably aramid STARAMID F-358 or PBO-HM.

[0072] In this invention, the epoxy resin-based resin is prepared by the following method: mixing epoxy resin, curing agent and accelerator and heating to obtain epoxy resin-based resin.

[0073] in:

[0074] The epoxy resin is preferably at least one of bisphenol A epoxy resins E-20, E-35, E-44, E-51 and multifunctional epoxy resin AG-80.

[0075] The curing agent is preferably dicyandiamide.

[0076] The accelerator is preferably an organic urea accelerator, more preferably at least one of UR300, UR500, and UR700.

[0077] The preferred dosage of the above-mentioned raw materials, by weight, is as follows: 80-88 parts epoxy resin, 8-10 parts curing agent, and 2-5 parts accelerator. Specifically, the epoxy resin can be 80, 81, 82, 83, 84, 85, 86, 87, or 88 parts. The curing agent can be 8, 9, or 10 parts, and the accelerator can be 2, 3, 4, or 5 parts.

[0078] The preferred heating temperature is 50–70°C, specifically 50°C, 55°C, 60°C, 65°C, or 70°C. After heating and mixing, an epoxy resin-based resin is obtained.

[0079] In this invention, the first composite material layer is preferably prepared by the following method: mixing epoxy resin-based resin and organic fiber, heating and curing to obtain the first composite material.

[0080] in:

[0081] The preferred mass ratio of epoxy resin-based resin to organic fiber is (43-54):100, specifically 43:100, 44:100, 45:100, 46:100, 47:100, 48:100, 49:100, 50:100, 51:100, 52:100, 53:100, and 54:100.

[0082] The preferred conditions for heat curing are: temperature 120–130℃, pressure 0.3–1.0 MPa, and time 1–3 hours. Specifically, the temperature can be 120℃, 121℃, 122℃, 123℃, 124℃, 125℃, 126℃, 127℃, 128℃, 129℃, or 130℃. The pressure can be 0.3 MPa, 0.4 MPa, 0.5 MPa, 0.6 MPa, 0.7 MPa, 0.8 MPa, 0.9 MPa, or 1.0 MPa. The time can be 1 hour, 2 hours, or 3 hours. After curing, the first composite material is obtained.

[0083] In this invention, the resin content in the first composite material layer is 30% to 35%, specifically 30%, 31%, 32%, 33%, 34%, or 35%.

[0084] In this invention, the modulus of the first composite material layer obtained at 20°C is as follows: flexural modulus ≥32GPa, storage modulus ≥24GPa.

[0085] In this invention, the thickness of the first composite material layer is preferably 2 to 8 mm, specifically 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, or 8 mm.

[0086] [Regarding the second composite material layer]:

[0087] In this invention, the second composite material layer is made of organic fibers and epoxy resin-based resin.

[0088] In this invention, the organic fiber used is a common modulus organic fiber, preferably a medium modulus grade fiber among aramid III fiber, PBO fiber, or polyimide fiber; the elastic modulus of the medium modulus grade fiber is 80-180 GPa, and the elastic modulus is lower than that of the organic fiber in the first composite material layer; specifically, it is preferably at least one of aramid STARAMID F-368, PBO-AS, polyimide fiber S30, and polyimide fiber S35.

[0089] In this invention, the epoxy resin-based resin is prepared by the following method: mixing epoxy resin, curing agent and accelerator and heating to obtain epoxy resin-based resin.

[0090] in:

[0091] The epoxy resin is preferably at least one of bisphenol A epoxy resins E-20, E-35, E-44, E-51 and multifunctional epoxy resin AG-80.

[0092] The curing agent is preferably dicyandiamide.

[0093] The accelerator is preferably an organic urea accelerator, more preferably at least one of UR300, UR500, and UR700.

[0094] The preferred dosage of the above-mentioned raw materials, by weight, is as follows: 80-88 parts epoxy resin, 8-10 parts curing agent, and 2-5 parts accelerator. Specifically, the epoxy resin can be 80, 81, 82, 83, 84, 85, 86, 87, or 88 parts. The curing agent can be 8, 9, or 10 parts, and the accelerator can be 2, 3, 4, or 5 parts.

[0095] The preferred heating temperature is 50–70°C, specifically 50°C, 55°C, 60°C, 65°C, or 70°C. After heating and mixing, an epoxy resin-based resin is obtained.

[0096] In this invention, the second composite material layer is preferably prepared by the following method: mixing epoxy resin-based resin and organic fiber, and heating and curing to obtain the second composite material.

[0097] in:

[0098] The preferred mass ratio of epoxy resin-based resin to organic fiber is (25-43):100, specifically 25:100, 26:100, 27:100, 28:100, 29:100, 30:100, 31:100, 32:100, 33:100, 34:100, 35:100, 36:100, 37:100, 38:100, 39:100, 40:100, 41:100, 42:100, and 43:100.

[0099] The preferred conditions for heat curing are: temperature 120–130℃, pressure 0.3–1.0 MPa, and time 1–3 hours. Specifically, the temperature can be 120℃, 121℃, 122℃, 123℃, 124℃, 125℃, 126℃, 127℃, 128℃, 129℃, or 130℃. The pressure can be 0.3 MPa, 0.4 MPa, 0.5 MPa, 0.6 MPa, 0.7 MPa, 0.8 MPa, 0.9 MPa, or 1.0 MPa. The time can be 1 hour, 2 hours, or 3 hours. After curing, a second composite material is obtained.

[0100] In this invention, the resin content in the obtained second composite material layer is 20% to 30%, specifically 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, and 30%.

[0101] In this invention, the modulus of the obtained second composite material layer at 20°C is as follows: flexural modulus 10–32 GPa, storage modulus 5–24 GPa. Specifically, the flexural modulus can be 10 GPa, 11 GPa, 12 GPa, 13 GPa, 14 GPa, 15 GPa, 16 GPa, 17 GPa, 18 GPa, 19 GPa, 20 GPa, 21 GPa, 22 GPa, 23 GPa, 24 GPa, 25 GPa, 26 GPa, 27 GPa, 28 GPa, 29 GPa, 30 GPa, 31 GPa, or 32 GPa. The specific energy storage modulus can be 5GPa, 6GPa, 7GPa, 8GPa, 9GPa, 10GPa, 11GPa, 12GPa, 13GPa, 14GPa, 15GPa, 16GPa, 17GPa, 18GPa, 19GPa, 20GPa, 21GPa, 22GPa, 23GPa, or 24GPa.

[0102] In this invention, the thickness of the second composite material layer is preferably 2 to 8 mm, specifically 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, or 8 mm.

[0103] [Regarding the third composite material layer]:

[0104] In this invention, the third composite material layer is made of organic fibers and epoxy resin modified polyvinyl butyral resin.

[0105] In this invention, the organic fiber used is a common modulus organic fiber, preferably a medium modulus grade fiber among aramid III fiber, PBO fiber, or polyimide fiber; the elastic modulus of the medium modulus grade fiber is 80-180 GPa, and the elastic modulus is lower than that of the organic fiber in the first composite material layer; specifically, it is preferably at least one of aramid STARAMID F-368, PBO-AS, polyimide fiber S30, and polyimide fiber S35.

[0106] In this invention, the epoxy resin modified polyvinyl butyral resin is prepared by the following method: epoxy resin, curing agent, polyvinyl butyral and diluent are mixed and dissolved, and then the diluent is removed by heating to obtain epoxy resin modified polyvinyl butyral resin.

[0107] in:

[0108] The epoxy resin is preferably at least one of bisphenol A epoxy resins E-20, E-35, E-44, E-51 and multifunctional epoxy resin AG-80.

[0109] The curing agent is preferably dicyandiamide.

[0110] The weight-average molecular weight of the polyvinyl butyral (PVB) is preferably 80,000 to 110,000, specifically 80,000, 90,000, 100,000, or 110,000.

[0111] The diluent is preferably a mixture of ethanol and isopropanol. The mass ratio of ethanol to isopropanol is preferably 1:1.

[0112] The preferred proportions of the above-mentioned raw materials by weight are as follows: 5-30 parts epoxy resin, 1-3 parts curing agent, 70-90 parts polyvinyl butyral, and 150 parts diluent. Specifically, the epoxy resin can be 5, 10, 15, 20, 25, or 30 parts. The curing agent can be 1, 2, or 3 parts. The polyvinyl butyral can be 70, 75, 80, 85, or 90 parts.

[0113] The above substances are stirred and dissolved evenly to obtain a matrix resin. Then, the diluent is removed by heating to obtain epoxy resin-modified polyvinyl butyral resin. The preferred heating temperature is 80–100°C, specifically 80°C, 85°C, 90°C, 95°C, or 100°C.

[0114] In this invention, the PVB content in the epoxy resin-modified polyvinyl butyral resin is preferably 70% to 95%, specifically 70%, 75%, 80%, 85%, 90%, or 95%.

[0115] In this invention, the third composite material layer is preferably prepared by the following method: mixing epoxy resin-modified polyvinyl butyral resin and organic fibers, and then heating and curing to obtain the third composite material.

[0116] in:

[0117] The preferred mass ratio of the epoxy resin-modified polyvinyl butyral resin to the organic fiber is (14-25):100, specifically 14:100, 15:100, 16:100, 17:100, 18:100, 19:100, 20:100, 21:100, 22:100, 23:100, 24:100, and 25:100.

[0118] The preferred conditions for heat curing are: temperature 150–165℃, pressure 0.5–1.0 MPa, and time 10–60 min. Specifically, the temperature can be 150℃, 151℃, 152℃, 153℃, 154℃, 155℃, 156℃, 157℃, 158℃, 159℃, 160℃, 161℃, 162℃, 163℃, 164℃, or 165℃. The pressure can be 0.5 MPa, 0.6 MPa, 0.7 MPa, 0.8 MPa, 0.9 MPa, or 1.0 MPa. The time can be 10 min, 20 min, 30 min, 40 min, 50 min, or 60 min. After curing, the third composite material is obtained.

[0119] In this invention, the resin content in the obtained third composite material layer is 12% to 20%, specifically 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, and 20%.

[0120] In this invention, the modulus of the obtained third composite material layer at 20°C is as follows: flexural modulus 2–10 GPa, storage modulus 0.5–5 GPa. Specifically, the flexural modulus can be 2 GPa, 3 GPa, 4 GPa, 5 GPa, 6 GPa, 7 GPa, 8 GPa, 9 GPa, or 10 GPa. The storage modulus can be 0.5 GPa, 1.0 GPa, 1.5 GPa, 2.0 GPa, 2.5 GPa, 3.0 GPa, 3.5 GPa, 4.0 GPa, 4.5 GPa, or 5.0 GPa.

[0121] In this invention, the thickness of the third composite material layer is preferably 2 to 5 mm, specifically 2 mm, 3 mm, 4 mm, or 5 mm.

[0122] In this invention, the three layers of materials (i.e., the first composite material layer, the second composite material layer, and the third composite material layer) are bonded together by adhesive film bonding; specifically, hot melt adhesive film is used for interlayer bonding, and the composite board is formed by hot pressing. The adhesive film is preferably a hot melt adhesive film, more preferably an EVA hot melt adhesive film, an EVA derivative hot melt adhesive film, a polyurethane resin hot melt adhesive film, or a polyolefin resin hot melt adhesive film. The preferred conditions for hot pressing are: temperature 90–120°C, pressure 0.6–1.0 MPa, and time 1–3 hours. Specifically, the temperature can be 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, or 120°C. The pressure can be 0.6 MPa, 0.7 MPa, 0.8 MPa, 0.9 MPa, or 1.0 MPa. The time can be 1 hour, 2 hours, or 3 hours.

[0123] This invention provides a gradient bulletproof and impact-resistant composite material, comprising, in sequence, a first composite material layer, a second composite material layer, and a third composite material layer; wherein the modulus of the first, second, and third composite material layers decreases sequentially; the modulus includes flexural modulus and storage modulus; the first composite material layer is made of organic fibers and epoxy resin-based resin; the modulus of the first composite material layer at 20°C is as follows: flexural modulus ≥ 32 GPa, storage modulus ≥ 24 GPa; the second composite material layer is made of organic fibers and epoxy resin-based resin; the modulus of the second composite material layer at 20°C is as follows: flexural modulus 10–32 GPa, storage modulus 5–24 GPa; the third composite material layer is made of organic fibers and epoxy resin-modified polyvinyl butyral resin; the modulus of the third composite material layer at 20°C is as follows: flexural modulus 2–10 GPa, storage modulus 0.5–5 GPa. The aforementioned gradient composite material exhibits a decreasing modulus (elastic modulus and storage modulus) and a gradually increasing flexibility from front to back, conforming to the mechanical response law under high-speed impact loads. It can fully utilize the characteristics of each layer of material, effectively improve the ultimate V50, and has broad application value in the field of armor protection.

[0124] To further understand the present invention, preferred embodiments of the present invention are described below in conjunction with examples. However, it should be understood that these descriptions are only for further illustrating the features and advantages of the present invention, and not for limiting the scope of the claims of the present invention.

[0125] Example 1

[0126] 1. First composite material layer:

[0127] It is made of organic fibers and epoxy resin.

[0128] in,

[0129] The organic fiber is aramid III fiber with a modulus of 145 GPa.

[0130] The epoxy resin-based resin was prepared by the following method: 88 parts of epoxy resin (E-51∶E-20=2∶3), 9 parts of dicyandiamide curing agent and 3 parts of UR300 accelerator were heated to 50℃ and stirred evenly to obtain the epoxy resin-based resin.

[0131] Epoxy resin-based resin and organic fiber were mixed at a mass ratio of 50:100 and cured at 120℃ and 0.8MPa for 1 hour to obtain the first composite material.

[0132] The thickness of the first composite material layer is 5 mm.

[0133] 2. Second composite material layer:

[0134] It is made of organic fibers and epoxy resin.

[0135] in,

[0136] The organic fiber is aramid III fiber with a modulus of 100 GPa.

[0137] The epoxy resin-based resin was prepared by the following method: 88 parts of epoxy resin (E-51∶E-20=2∶3), 9 parts of dicyandiamide curing agent and 3 parts of UR300 accelerator were heated to 50℃ and stirred evenly to obtain the epoxy resin-based resin.

[0138] Epoxy resin-based resin and organic fiber were mixed at a mass ratio of 40:100 and cured at 120℃ and 0.8MPa for 1 hour to obtain the second composite material.

[0139] The thickness of the second composite material layer is 3 mm.

[0140] 3. Third composite material layer:

[0141] It is made of polyvinyl butyral resin modified with organic fibers and epoxy resin.

[0142] in,

[0143] The organic fiber is aramid III fiber with a modulus of 100 GPa.

[0144] Epoxy-modified polyvinyl butyral resin is prepared by the following method: 25 parts of E-35 epoxy resin, 2 parts of dicyandiamide curing agent, 75 parts of PVB resin with a molecular weight of 80,000 and 150 parts of diluent (mass ratio of ethanol to isopropanol = 1:1) are mixed and dissolved, and then the diluent is removed by heating to obtain epoxy-modified PVB resin.

[0145] Epoxy-modified PVB and organic fibers were mixed at a mass ratio of 18:100 and cured at 165℃ and 1.0MPa for 10 minutes to obtain the third composite material.

[0146] The thickness of the third composite material layer is 3 mm.

[0147] 4. Preparation of composite board:

[0148] The first composite material layer, the second composite material layer, and the third composite material layer are bonded together using EVA hot melt adhesive film, and then hot-pressed at 120℃ and 0.8MPa for 1 hour to obtain a gradient bulletproof and impact-resistant composite material.

[0149] Example 2

[0150] 1. First composite material layer:

[0151] It is made of organic fibers and epoxy resin.

[0152] in,

[0153] The organic fiber is PBO-HM fiber with a modulus of 280 GPa.

[0154] The epoxy resin-based resin is prepared by the following method: 90 parts of E-35 epoxy resin, 8 parts of dicyandiamide curing agent and 2 parts of UR400 accelerator are heated to 60°C and stirred evenly to obtain the epoxy resin-based resin.

[0155] Epoxy resin-based resin and organic fiber were mixed at a mass ratio of 50:100 and cured at 130℃ and 0.6MPa for 2 hours to obtain the first composite material.

[0156] The thickness of the first composite material layer is 3 mm.

[0157] 2. Second composite material layer:

[0158] It is made of organic fibers and epoxy resin.

[0159] in,

[0160] The organic fiber is PBO-AS fiber with a modulus of 180 GPa.

[0161] The epoxy resin-based resin was prepared by the following method: 88 parts of epoxy resin (E-51∶E-20=2∶3), 9 parts of dicyandiamide curing agent and 3 parts of UR300 accelerator were heated to 60℃ and stirred evenly to obtain the epoxy resin-based resin.

[0162] Epoxy resin-based resin and organic fiber were mixed at a mass ratio of 40:100 and cured at 120℃ and 0.8MPa for 2 hours to obtain the second composite material.

[0163] The second composite material layer has a thickness of 4 mm.

[0164] 3. Third composite material layer:

[0165] It is made of polyvinyl butyral resin modified with organic fibers and epoxy resin.

[0166] in,

[0167] The organic fiber is aramid III fiber with a modulus of 100 GPa.

[0168] Epoxy-modified polyvinyl butyral resin is prepared by the following method: 35 parts of E-35 epoxy resin, 3 parts of dicyandiamide curing agent, 65 parts of PVB resin with a molecular weight of 110,000 and 150 parts of diluent (mass ratio of ethanol to isopropanol = 1:1) are mixed and dissolved, and then the diluent is removed by heating to obtain epoxy-modified PVB resin.

[0169] Epoxy-modified PVB and organic fibers were mixed at a mass ratio of 18:100 and cured at 160℃ and 0.6MPa for 60 minutes to obtain the third composite material.

[0170] The thickness of the third composite material layer is 4 mm.

[0171] 4. Preparation of composite board:

[0172] The first composite material layer, the second composite material layer, and the third composite material layer are bonded together using EVA hot melt adhesive film, and then hot-pressed at 90℃ and 1.0MPa for 2 hours to obtain a gradient bulletproof and impact-resistant composite material.

[0173] Example 3

[0174] 1. First composite material layer:

[0175] It is made of organic fibers and epoxy resin.

[0176] in,

[0177] The organic fiber is PBO-HM fiber with a modulus of 280 GPa.

[0178] The epoxy resin-based resin is prepared by the following method: 90 parts of epoxy resin (E-44∶E-20=2∶2), 8 parts of dicyandiamide curing agent and 2 parts of UR500 accelerator are heated to 60℃ and stirred evenly to obtain the epoxy resin-based resin.

[0179] Epoxy resin-based resin and organic fiber were mixed at a mass ratio of 45:100 and cured at 120℃ and 0.8MPa for 3 hours to obtain the first composite material.

[0180] The thickness of the first composite material layer is 3 mm.

[0181] 2. Second composite material layer:

[0182] It is made of organic fibers and epoxy resin.

[0183] in,

[0184] The organic fiber is aramid III fiber with a modulus of 100 GPa.

[0185] The epoxy resin-based resin was prepared by the following method: 88 parts of epoxy resin (E-44∶E-20=2∶2), 9 parts of dicyandiamide curing agent and 3 parts of UR300 accelerator were heated to 60℃ and stirred evenly to obtain the epoxy resin-based resin.

[0186] Epoxy resin-based resin and organic fiber were mixed at a mass ratio of 30:100 and cured at 130℃ and 0.5MPa for 1 hour to obtain the second composite material.

[0187] The thickness of the second composite material layer is 3 mm.

[0188] 3. Third composite material layer:

[0189] It is made of polyvinyl butyral resin modified with organic fibers and epoxy resin.

[0190] in,

[0191] The organic fiber is aramid III fiber with a modulus of 100 GPa.

[0192] Epoxy-modified polyvinyl butyral resin is prepared by the following method: 15 parts of epoxy resin (E-51∶E-20=2∶3), 2 parts of dicyandiamide curing agent, 85 parts of PVB resin with a molecular weight of 100,000 and 150 parts of diluent (ethanol∶isopropanol mass ratio=1∶1) are mixed and dissolved, and then the diluent is removed by heating to obtain epoxy-modified PVB resin.

[0193] Epoxy-modified PVB and organic fibers were mixed at a mass ratio of 15:100 and cured at 150℃ and 1.0MPa for 40 minutes to obtain the third composite material.

[0194] The thickness of the third composite material layer is 5 mm.

[0195] 4. Preparation of composite board:

[0196] The first composite material layer, the second composite material layer, and the third composite material layer are bonded together using a polyolefin hot melt adhesive film, and then hot-pressed at 110℃ and 1.0MPa for 2 hours to obtain a gradient bulletproof and impact-resistant composite material.

[0197] Example 4

[0198] 1. First composite material layer:

[0199] It is made of organic fibers and epoxy resin.

[0200] in,

[0201] The organic fiber is aramid III fiber with a modulus of 145 GPa.

[0202] The epoxy resin-based resin is prepared by the following method: 90 parts of epoxy resin (E-44∶AG-80=4∶1), 8 parts of dicyandiamide curing agent and 2 parts of UR500 accelerator are heated to 70℃ and stirred evenly to obtain the epoxy resin-based resin.

[0203] Epoxy resin-based resin and organic fiber were mixed at a mass ratio of 52:100 and cured at 120℃ and 1.0MPa for 2 hours to obtain the first composite material.

[0204] The thickness of the first composite material layer is 7 mm.

[0205] 2. Second composite material layer:

[0206] It is made of organic fibers and epoxy resin.

[0207] in,

[0208] The organic fiber is aramid III fiber with a modulus of 125 GPa.

[0209] The epoxy resin-based resin was prepared by the following method: 88 parts of epoxy resin (E-44∶E-20=2∶2), 9 parts of dicyandiamide curing agent and 3 parts of UR300 accelerator were heated to 70℃ and stirred evenly to obtain the epoxy resin-based resin.

[0210] Epoxy resin-based resin and organic fiber were mixed at a mass ratio of 30:100 and cured at 120℃ and 0.8MPa for 2 hours to obtain the second composite material.

[0211] The thickness of the second composite material layer is 2 mm.

[0212] 3. Third composite material layer:

[0213] It is made of polyvinyl butyral resin modified with organic fibers and epoxy resin.

[0214] in,

[0215] The organic fiber is a polyimide fiber with a modulus of 100 GPa.

[0216] Epoxy-modified polyvinyl butyral resin is prepared by the following method: 20 parts of epoxy resin (E-44∶E-20=2∶2), 2 parts of dicyandiamide curing agent, 80 parts of PVB resin with a molecular weight of 100,000 and 150 parts of diluent (ethanol∶isopropanol mass ratio=1∶1) are mixed and dissolved, and then the diluent is removed by heating to obtain epoxy-modified PVB resin.

[0217] Epoxy-modified PVB and organic fibers were mixed at a mass ratio of 20:100 and cured at 160℃ and 0.8MPa for 20 minutes to obtain the third composite material.

[0218] The thickness of the third composite material layer is 2 mm.

[0219] 4. Preparation of composite board:

[0220] The first composite material layer, the second composite material layer, and the third composite material layer are bonded together using EVA hot melt adhesive film, and then hot-pressed at 160℃ and 0.6MPa for 3 hours to obtain a gradient bulletproof and impact-resistant composite material.

[0221] Comparative Example 1

[0222] A general modulus organic fiber composite material reinforced with epoxy resin.

[0223] The organic fiber is aramid III fiber with a modulus of 125 GPa.

[0224] The epoxy resin-based resin was prepared by the following method: 88 parts of epoxy resin (E-51∶E-20=2∶3), 9 parts of dicyandiamide curing agent and 3 parts of UR300 accelerator were heated to 70℃ and stirred evenly to obtain the epoxy resin-based resin.

[0225] Epoxy resin-based resin and organic fiber were mixed at a mass ratio of 40:100 and cured at 120℃ and 0.8MPa for 2 hours to obtain a composite material.

[0226] The composite material layer is 11 mm thick.

[0227] Product testing:

[0228] Referring to the GA / T 950-2019 Test Method for V50 of Ballistic Materials and Products, the ballistic limit V50 of the composite materials obtained in the examples and comparative examples was tested, and the test results are shown in Table 1.

[0229] Table 1: Test Results

[0230]

[0231] It can be seen that Comparative Example 1 is an epoxy resin-based composite material without gradient change, with a V50 of 723 m / s. Examples 1 to 4 are composite materials with different gradient structures. Compared with Comparative Example 1, the V50 is increased to over 767 m / s, which fully utilizes the performance advantages of each layer of composite material in the gradient structure.

[0232] This document uses specific examples to illustrate the principles and implementation methods of the present invention. The descriptions of these embodiments are merely to aid in understanding the method and core ideas of the present invention, including the best mode, and to enable any person skilled in the art to practice the present invention, including manufacturing and using any device or system, and implementing any combined method. It should be noted that those skilled in the art can make various improvements and modifications to the present invention without departing from its principles, and these improvements and modifications also fall within the scope of protection of the claims. The scope of protection of this patent is defined by the claims and may include other embodiments that can be conceived by those skilled in the art. If these other embodiments have structural elements similar to those expressed in the claims, or if they include equivalent structural elements that are not substantially different from those expressed in the claims, then these other embodiments should also be included within the scope of the claims.

Claims

1. A gradient bulletproof and impact-resistant composite material, characterized in that, It includes, in sequence, a first composite material layer, a second composite material layer, and a third composite material layer; The modulus of the first composite material layer, the second composite material layer, and the third composite material layer decreases sequentially; the modulus includes flexural modulus and storage modulus. The first composite material layer is made of organic fiber and epoxy resin; the modulus of the first composite material layer at 20°C is as follows: flexural modulus ≥32GPa, storage modulus ≥24GPa; The second composite material layer is made of organic fibers and epoxy resin; the modulus of the second composite material layer at 20°C is as follows: flexural modulus 10~32GPa, storage modulus 5~24GPa; The third composite material layer is made of organic fiber and epoxy resin modified polyvinyl butyral resin; the modulus of the third composite material layer at 20°C is as follows: flexural modulus 2~10GPa, storage modulus 0.5~5GPa.

2. The gradient bulletproof and impact-resistant composite material according to claim 1, characterized in that, In the first composite material layer: The epoxy resin-based resin is prepared by the following method: mixing epoxy resin, curing agent and accelerator and heating to obtain epoxy resin-based resin; in: The epoxy resin is at least one of bisphenol A epoxy resins E-20, E-35, E-44, E-51 and multifunctional epoxy resin AG-80; The curing agent is dicyandiamide; The accelerator is an organic urea accelerator; The proportions of the above raw materials by weight are as follows: epoxy resin 80-88 parts, curing agent 8-10 parts, accelerator 2-5 parts; The heating temperature is 50~70℃; In the second composite material layer: The epoxy resin-based resin is prepared by the following method: mixing epoxy resin, curing agent and accelerator and heating to obtain epoxy resin-based resin; in: The epoxy resin is at least one of bisphenol A epoxy resins E-20, E-35, E-44, E-51 and multifunctional epoxy resin AG-80; The curing agent is dicyandiamide; The accelerator is an organic urea accelerator; The proportions of the above raw materials by weight are as follows: epoxy resin 80-88 parts, curing agent 8-10 parts, accelerator 2-5 parts; The heating temperature is 50~70℃.

3. The gradient bulletproof and impact-resistant composite material according to claim 1, characterized in that, In the third composite material layer: The epoxy resin modified polyvinyl butyral resin is prepared by the following method: epoxy resin, curing agent, polyvinyl butyral and diluent are mixed and dissolved, and then the diluent is removed by heating to obtain epoxy resin modified polyvinyl butyral resin. in: The epoxy resin is at least one of bisphenol A epoxy resins E-20, E-35, E-44, E-51 and multifunctional epoxy resin AG-80; The curing agent is dicyandiamide; The weight-average molecular weight of the polyvinyl butyral is 80,000 to 110,000. The diluent is a mixture of ethanol and isopropanol; The proportions of the above raw materials by weight are as follows: epoxy resin 5-30 parts, curing agent 1-3 parts, polyvinyl butyral 70-90 parts, and diluent 150 parts.

4. The gradient bulletproof and impact-resistant composite material according to claim 1, characterized in that, In the first composite material layer, the organic fiber is a high-modulus grade fiber among aramid III fiber, PBO fiber or polyimide fiber, and the elastic modulus of the high-modulus grade fiber is 140~280GPa. In the second composite material layer, the organic fiber is a medium modulus grade fiber among aramid III fiber, PBO fiber, or polyimide fiber; the elastic modulus of the medium modulus grade fiber is 80~180GPa, and the elastic modulus is lower than that of the organic fiber in the first composite material layer. In the third composite material layer, the organic fiber is a medium modulus grade fiber among aramid III fiber, PBO fiber, or polyimide fiber; the elastic modulus of the medium modulus grade fiber is 80~180GPa, and the elastic modulus is lower than that of the organic fiber in the first composite material layer.

5. The gradient bulletproof and impact-resistant composite material according to claim 4, characterized in that, In the first composite material layer, the organic fiber is aramid STARAMID F-358 or PBO-HM; In the second composite material layer, the organic fiber is at least one of aramid STARAMID F-368, PBO-AS, polyimide fiber S30, and polyimide fiber S35; In the third composite material layer, the organic fiber is at least one of aramid STARAMID F-368, PBO-AS, polyimide fiber S30, and polyimide fiber S35.

6. The gradient bulletproof and impact-resistant composite material according to claim 1, characterized in that, The first composite material layer is prepared by mixing epoxy resin and organic fiber, and then heating and curing to obtain the first composite material. in: The mass ratio of the epoxy resin-based resin to the organic fiber is (43~54):100; The conditions for heat curing are: temperature 120~130℃, pressure 0.3~1.0MPa, and time 1~3h.

7. The gradient bulletproof and impact-resistant composite material according to claim 1, characterized in that, The second composite material layer is prepared by mixing epoxy resin-based resin and organic fibers, and then heating and curing to obtain the second composite material. in: The mass ratio of the epoxy resin-based resin to the organic fiber is (25~43):100; The conditions for heat curing are: temperature 120~130℃, pressure 0.3~1.0MPa, and time 1~3h.

8. The gradient bulletproof and impact-resistant composite material according to claim 1, characterized in that, The third composite material layer is prepared by the following method: epoxy resin modified polyvinyl butyral resin and organic fiber are mixed and cured by heating to obtain the third composite material; in: The mass ratio of the epoxy resin-modified polyvinyl butyral resin to the organic fiber is (14~25):

100. The conditions for heat curing are: temperature 150~165℃, pressure 0.5~1.0MPa, and time 10~60min.

9. The gradient bulletproof and impact-resistant composite material according to claim 1, characterized in that, The thickness of the first composite material layer is 2~8mm; The thickness of the second composite material layer is 2~8mm; The thickness of the third composite material layer is 2~5mm.

10. The gradient bulletproof and impact-resistant composite material according to claim 1, characterized in that, The gradient bulletproof and impact-resistant composite material is prepared by the following method: A composite board is formed by hot-melt adhesive film bonding between the first composite material layer, the second composite material layer and the third composite material layer, and hot-pressing the composite material together. The conditions for hot-press composite molding are: temperature 90~120℃, pressure 0.6~1.0MPa, and time 1~3h.

Images