Light-weight bulletproof plate with high performance process

Abstract

The present invention relates to a light-weight bulletproof plate with high performance, comprising thermoplastic polymer sheet, particularly high molecular density polyethylene which has specific stacking of fibre of this invention. Embedded graphene is provided and co-extruded with polymer sheet with heat and extrusion force, then cooling, partitioning the edge of extruded polymer from with foam, attaching honeycomb fabric and ceramic plate respectively, and covering with a single or double weave fabric carbon fibre. The composite is prepared by vacuum infusion under closed system, which the liquid matrix is epoxy resin or epoxy resin with graphene, and hardened under vacuum condition before use.

Description

[0001] LIGHT-WEIGHT BULLETPROOF PLATE WITH HIGH PERFORMANCE PROCESS

[0002] Field of the invention

[0003] Chemistry, material science, and chemical engineering, especially related to light-weight bulletproof plate with high performance process.

[0004] Background of the invention

[0005] A bulletproof vest is essential equipment for protecting individuals from impact or reducing or stopping the impact of bullets penetrating into the body. Previously, bulletproof vest was primarily made of metal, which is heavy and hampered personnel in their work. Later, ceramic armor has been developed and used instead of metal which is lighter. However, ceramics are still heavy and may be shattered or cracked when getting the impact, which is danger to both the wearer and people nearby. In the case of a collision with a high-performance 7.62 mm NATO FMJ 148 Gr. bullet with a bullet velocity of 847 ± 9.1 meters / second, the ceramic plates would not be able to withstand the impact of six bullets in a single plate. Therefore, bulletproof vests have been developed by using polymer as protective materials, particularly thermoplastic polymers such as ultra-high molecular weight polyethylene, due to their ability to easily change their structure when received force or heat. Since the absence of cross-linking between molecular chains, this polymer possesses excellent mechanical and physical properties, including strength, flexibility, light weight, high impact resistance, and resistance to humid and hot environments. It can be formed into polymer sheets with other strengthening materials, or coated with materials or composites to enhance its functional properties, for example, graphene which exhibits extremely high strength. At the same thickness, graphene is stronger than steel and offers high flexibility, allowing it to be easily bent, rolled, or folded without damaging the molecules.

[0006] For patent database, we found that high molecular density polyethylene stacking by attaching with heat and extruding force. Below is the examples.

[0007] CN204612597U, “Armour”, discloses the attachment of high molecular density polyethylene with heat and knitting.

[0008] CN102519311 A, “a preparing method of ultra-high molecular weight polyethylene bulletproof plate”, discloses steps of more than one stacking and attaching of synthetic fibre sheet of high molecular density polyethylene with 5-10 MPa of extrusion force, 80-100 degree Celsius of temperature, for 20-30 minutes, and attaching of sheet with 25-30 MPa of extrusion force and 140 degree Celsius of temperature. CA2515868A1, “Multilayer polyethylene material and ballistic resistant articles manufactured therefrom”, discloses a step of stacking without binder of high molecular density polyethylene with 0.1-1 MPa of extrusion force, and 100-150 degree Celsius of temperature.

[0009] The prior arts related to polyethylene sheet coated with graphene and process of coating are shown in the example below.

[0010] WO2014197082A2, “Gradient nanoparticle-carbon allotrope-polymer composite material”, and WO2012054472A2, “Gradient nanoparticle-carbon allotrope-polymer composite material”, disclose the coating with carbon compound including graphene on surface of high molecular density polyethylene synthetic fibre.

[0011] The prior arts related to polyethylene sheet with high molecular density polyethylene as component and layer having stacking graphene, and process by attaching with extrusion force and heat. Here is the examples.

[0012] CA2966512A1, “soft ballistic resistance armor”, discloses a soft armor having composite sheet with high molecular density polyethylene fibre stacking between graphene. The composite is coat with silicone as interlayer and attached with 14-28 MPa of extrusion force with 93-150 degree Celsius of temperature.

[0013] CN107471791 A, “A graphene-reinforced composite ballistic plate and preparation method thereof’, discloses a stacking of high molecular density polyethylene fibre with olefin sheet mixing with graphene and attached with 16-25 MPa of extrusion force with 70-130 degree Celsius of temperature for 30 minutes.

[0014] According to the prior art mentioned above, it is obvious that the development of bulletproof using high-molecular density polyethylene synthetic fibre sheets by coating graphite on the polymer sheets to increase their strength, together with attaching with extrusion force and heat under different conditions. This invention discloses a process for developing high- performance, lightweight bulletproof by embedding graphene into polymer sheets, specifically high-molecular density polyethylene, in one-step and inexpensive process. The graphene is then stacked and extruded by using specified extrusion force and heat. By assembling a composite structure in the specific form of this invention, the product has been tested to withstand impact from six rounds of high-performance 7.62 mm NATO FMJ 148 Gr. rounds with a bullet velocity of 847 ± 9.1 m / s within a single sheet, and to withstand impact from a high-performance .30 caliber M2 AP 166 Gr. round with a bullet velocity of 878 ± 9.1 m / s. Summary of the invention

[0015] This invention is directly related to a high-performance, lightweight bulletproof comprising polymer sheets, particularly high molecular density polyethylene, with graphene which is embedded in the polymer sheets, particularly high molecular weight polyethylene, in one-step inexpensive process. The polymer sheets are stacked at least 40 layers, attached by extrusion force and heat as specified, cooled, partitioned the edge with foam around the edges of the polymer sheets, attached to a honeycomb fabric and a ceramic sheet having the dimensions and arrangement as specified in the present invention, covered with a carbon fibre woven fabric by attaching with a thermosetting plastic matrix, particularly an epoxy resin, allowed to harden under vacuum condition by a vacuum infusion system, and then covered with fabrics which is able to be screen-printed to clearly display symbols or emblems for convenience and beauty. The lightweight and high-performance bulletproof is obtained.

[0016] This invention aims to provide a lightweight, high-performance bulletproof vest obtained by a one-step, and inexpensive process from embedded graphene in polymers, particularly high molecular density polyethylene polymer, and then stacking and extruding them under specified extrusion force and heat. The composite structure is then assembled with honeycomb fabrics and ceramic sheets, and covered with a carbon fibre woven fabric in a specific configuration of this invention. The product has been tested to withstand the impact of six rounds of a 7.62 mm NATO FMJ 148 Gr. high-performance bullet with a bullet velocity of 847 ± 9.1 m / s within a single sheet, and to withstand the impact of a .30 caliber M2 AP 166 Gr. high-performance bullet with a bullet velocity of 878 ± 9.1 m / s. The results show high strength, rigidity, and high impact resistance, and is safe from cracks and fractures from the ceramic sheets when used by officers and nearby personnel.

[0017] Various purposes and features of the present invention will become clearer when considered together with the accompanying drawings and the best detailed description of the invention which will be described below.

[0018] Brief description of the drawings

[0019] The accompanying drawings, which are included herein to provide a further understanding of the present disclosure and are incorporated herein to constitute a part of the present specification. The accompanying drawings illustrate embodiments of the present disclosure and are used in conjunction with the following description to illustrate the concepts of the present disclosure. Figure 1 illustrates one-step ultrasonic mixing system according to the present invention.

[0020] Figure 2 illustrates composite structural sheet formed into high performance, lightweight, bulletproof plates according to the present invention.

[0021] Detailed description of the invention

[0022] This description of this invention will be made by illustrating the invention and referring to it by means of drawings and photographs to illustrate and clarify the description, and identical parts in these drawings will be represented by the same reference numbers. This is without any limitation and the scope of the invention will be in accordance with the appended claims.

[0023] A formula and process for developing a high-performance, lightweight bulletproof comprising polymer sheets with embedded graphene, particularly high molecular weight polyethylene, in one-step inexpensive process. The polymer sheets are then arranged along the fibre direction and attached under specified extrusion force and heat, and stacked and extruded under extrusion force and heat. The formula and process for embedding graphene in composite structure sheets are then assembled with honeycomb fabrics, ceramic sheets, and carbon fibre woven fabrics in a closed system that is environmentally -friendly and inexpensive in a unique form of this invention.

[0024] A formula and process for developing a high-performance, lightweight bulletproof is provided by thermoplastic polymer selected from polystyrene, polyethylene, polypropylene, polyvinyl chloride, nylon, polyamide, polyacrylonitrile, or a combination thereof, preferably polyethylene, and more preferably high molecular weight polyethylene. The process includes the steps of:

[0025] (A) Mixing 1-15% by weight of binder with 1-10% by weight of graphene in container. The binder is selected from polytetrafluoroethylene, polyvinylidene fluoride, CERACOL 607, polyethylene, or a combination thereof, preferably polyethylene.

[0026] (B) The graphene is functionalized by functional groups which selected from oxygen, nitrogen, ammonia, carboxylic, argon, or a combination thereof, preferably carboxylic group. The graphene is plasma-polymerized for improving surface of materials via making the molecule of gas is in state of instability and constantly excited as ions electrons which reacts to material surface or substrate to form a thin film attached to the surface within the reactor.

[0027] (C) Mixing 0.1-5% by weigh of dispersing agent into the mixtures of step (B) in order to assist to disperse the mixture and prevent the agglomeration and precipitation. The dispersing agent is selected from arylate copolymer, acrylate derivatives, polar compound, Affinic, carboxylic derivatives, arylate compound, arylate copolymer BVK-112, or a combination thereof, preferably arylate copolymer BVK-112.

[0028] (D) Mixing 85-95% by weight of liquid matrix into the mixtures of step (C). The liquid matrix is thermosetting polymer selected from polyurethane resin, phenolic resin, urea formaldehyde resin, melamine formaldehyde resin, polyester resin, epoxy resin, or a combination thereof, preferably epoxy resin.

[0029] (E) Homogenising mixtures of step (D) by using one-step ultrasonic homogeniser in order that the molecule in graphene as nanoparticles in mixtures is arranged in vertical direction, which causes high efficiency in dispersion of mixtures with graphene in viscous liquid of thermosetting plastic, particularly epoxy resin and increases the efficiency of functionalized graphene with carboxylic group serves as crosslinking hydrogen bond with thermosetting plastic, particularly epoxy resin. The one-step ultrasonic mixing system is provided in Figure 1, which comprises a cooling tank (100) for containing mixtures, connecting with a progressive cavity pump (200) that facilitates the high-viscosity mixtures flow to the system, the system also provides a cooling system (300) for controlling temperature of liquid mixture in the range of 27-55 degree Celsius, and controlling pressure by pressure gauge before into a flow cell (400) that serves as to input the liquid mixture into an ultrasonic source (500), including ultrasonic generator and ultrasonic transducer, with frequency 20-40 kHz, amplitude 50-100%, and energy 2 kW, and flows the homogenised liquid mixtures a cooling tank (600) via duct.

[0030] (F) The fibre in roll form is arranged, and a fibre roller is provided as device for controlling fibre tension overall the system. The fibre is selected from polystyrene, polyethylene, polypropylene, polyvinyl chloride, nylon, polyamide, polyacrylonitrile, or a combination thereof, preferable polyethylene, and more preferable high molecular density polyethylene polymer. Then, the polymer fibre is immerged in liquid mixtures from step (E) in the container and extruded the excess liquid via roller. The liquid mixtures are provided in 5-15% by weight, the extrusion force is provided in 1-5 MPa, the temperature in the system is provided in 45-65 degree Celsius. The polymer sheet is cooled at 25-35 degree Celsius in order that graphene is embedded in the polymer sheet with one-direction fibre.

[0031] Next, the polymer sheet embedded with graphene is co -extruded with polymer sheet without embedded graphene. The process includes the steps of:

[0032] 1) Stacking at least 2 polymer sheets or more with embedded graphene, having 0 / 90 degree of fibre in longitudinal and vertical direction, and stacking at least 2 polymer sheets or more without embedded graphene, having 0 / 90 degree of fibre in longitudinal and vertical direction. 2) Stacking polymer from step 1) is arranged by the polymer sheet with embedded graphene is provided on the outer radius curve (001) and the polymer sheet without embedded graphene is provided on the inner radius curve (002), and then the polymer sheets are extruded into a metal mold according to shape of bulletproof via hot transfer molding pressure with temperature of 120-140 degree Celsius, and extrusion force of 5-15 mPa for 10-30 minutes. The temperature is set to upper mold, lower mold, or a combination thereof.

[0033] 3) The extruded polymer sheet is cooled within metal mold under extrusion force of 5-15 mPa, with temperature of 50-70 degree Celsius.

[0034] Next, the extruded polymer is assembled to composite structure according to Figure 2. The process includes the steps of:

[0035] (A) Partitioning the edge of extruded polymer with foam (003) with 6- 10 mm. thickness and 15-25 mm. width, and attaching with epoxy glue on the outer radius curve (001). The foam (003) is selected from rubber foam, polyvinyl chloride foam with plasticizer, polyurethane foam, polyolefin foam, polystyrene foam, polycarbonate foam, polyphenolic foam, polyethylene foam, or a combination thereof.

[0036] (B) Attaching honeycomb fabric (004) having 1-2 mm. thickness of polyester onto extruded polymer from step (A) by spray glue within foam edge of the outer radius curve in order to increase the flow of epoxy resin and attachment efficiency of surface between extruded polymer sheet with embedded graphene and ceramic plate.

[0037] (C) 20 ceramic plates (005) which is rectangle shape with 25-50 mm. width, 40-50 mm. length, and 6-10 mm. thickness, and the 2 ceramic plates (005) which is triangle shape with a base and height of 40-50 mm., and 6-10 mm. thickness are attached onto extruded polymer sheet from step (B) with foam edge of the outer radius curve by spray glue. The ceramic plate (005) is selected from silicon carbide, boron carbide, or a combination thereof.

[0038] (D) The extruded polymer sheet from step (C) are covered with a single or double weave fabric (006) having 160-240 g / m2, and attached with spray glue. The single or double weave fabric (006) is selected from carbon fibre, glass fibre, aramid, or a combination thereof, with 160-240 g / m2, preferably carbon fibre.

[0039] (E) The composite structure from step (D) is moled via vacuum infusion mold in closed system, which is safe and environmental-friendly. The lower mold is polymer reinforced fiberglass with 15-25 mm. of hole deepness, and 15-20 mm. of center of curve height, and the upper mold is silicone. The liquid matrix is provided as thermoplastic polymer and selected from polyurethane resin, phenolic resin, urea formaldehyde resin, melamine formaldehyde resin, polyester resin, epoxy resin, epoxy resin mixing with graphene, or a combination thereof, preferable is epoxy resin or epoxy resin mixing with graphene. The flow of resin is 10-20 minutes.

[0040] (F) The composite structure from step (E) is hardened under vacuum condition for 3-8 hours. The product of light-weight bulletproof plate with high performance is obtained with 1.8- 2.2 kilograms shown in Figure 2, covered with fabrics which is able to be screen-printed to clearly display symbols or emblems for convenience and beauty.

[0041] Example of the impact resistance of a high-performance 7.62 mm NATO FMJ 148 Gr. Bullet, the bullet velocity of 847+9.1 m / s with a firing angle of 0 degrees of sample plate 1 is shown in Table 1.

[0042] In the table 2, test results of sample 1 are subjected to impact force from high performance bullets 7.62 mm NATO FMJ 148 Gr. velocity of the bullet 847+9.1 m / s with a firing angle of 0 degrees, 6 rounds in the same plate.

[0043] Table 1: Example of the impact resistance of a high-performance bullets of sample plate 1.

[0044] Example of the impact resistance of a high-performance .30 caliber M2 AP 166 Gr. Bullet, the bullet velocity of 878+9.1 m / s with 0 degree firing angle of sample plate 2 and 3 are shown in Table 2.

[0045] In the table 2, test results of examples 2 and 3 are subjected to impact from a high- performance bullet, caliber .30 caliber M2 AP 166 Gr., the bullet velocity 878+9.1 m / s, firing angle 0 degrees, 1 round. Table 2: Example of the impact resistance of a high-performance bullets of sample plate 2 and 3.

[0046] Although the present invention has been described in detailed description by means of the attached drawings, it is understood that modifications or alterations by a person who skilled in the art and science, within the scope and purpose of the invention, can be made. The scope of the present invention shall be in accordance with the embodiment of the invention as stated in the appended claims, including aspects of the invention, although it is not specifically stated in the claims, have a utility and produce results similar to those of the invention as stated in the claims.

[0047] Best mode for carrying out the invention Best mode or preferred embodiment of the invention is as provided in the description of the invention.

Claims

Claims1. A light-weight bulletproof plate with high performance, comprising polymer sheet with embedded graphene (001) co-extruded with polymer sheet without embedded graphene (002), partitioned the edge with foam (003), attached with honeycomb fabric (004), attached with ceramic plate (005), and entirely covered with a single or double weave fabric (006), having composite structure with embedded graphene of 1-10% by weight.

2. The bulletproof plate as claimed in claim 1, wherein polymer sheet with embedded graphene (001) includes polymer fibre having liquid matrix mixing with graphene.

3. The bulletproof plate as claimed in claim 2, wherein polymer fibre is thermoplastic polymer selected from polystyrene, polyethylene, polypropylene, polyvinyl chloride, nylon, polyamide, polyacrylonitrile, or a combination thereof.

4. The bulletproof plate as claimed in claims 3, wherein polymer fibre is high molecular density polyethylene.

5. The bulletproof plate as claimed in claim 2, wherein liquid matrix mixing with graphene formulation comprises:- Graphene 1-10% by weight- Binder 1-15% by weight- Dispersing agent 0.1-5% by weight- Liquid matrix 85-95% by weight- all components are mixed to complete 100% by weight.

6. The bulletproof plate as claimed in claim 5, wherein graphene have functional groups selected from oxygen, nitrogen, ammonia, carboxylic, argon, or a combination thereof.

7. The bulletproof plate as claimed in claim 6, wherein graphene have carboxylic functional group.

8. The bulletproof plate as claimed in claim 5, wherein the binder is selected from polytetrafluoroethylene, poly vinylidene fluoride, CERACOL 607, polyethylene, or a combination thereof.

9. The bulletproof plate as claimed in claim 8, wherein the binder is polyethylene10. The bulletproof plate as claimed in claim 5, wherein the dispersing agent is selected from arylate copolymer, acrylate derivatives, polar compound, Affinic, carboxylic derivatives, arylate compound, arylate copolymer BVK-112, or a combination thereof.

11. The bulletproof plate as claimed in claim 10, wherein the dispersing agent is arylate copolymer B VK- 112.

12. The bulletproof plate as claimed in claim 5, wherein the liquid matrix is thermosetting polymer selected from polyurethane resin, phenolic resin, urea formaldehyde resin, melamine formaldehyde resin, polyester resin, epoxy resin, or a combination thereof.

13. The bulletproof plate as claimed in claim 12, wherein the liquid matrix is epoxy resin.

14. The bulletproof plate as claimed in claim 2, wherein the liquid matrix mixing with graphene is prepared from the step comprising:(A) Mixing binder with functionalized graphene.(B) Mixing dispersing agent into the mixtures of step (A).(C) Mixing liquid matrix into the mixtures of step (B).(D) Homogenising mixtures of step (C) by using one-step ultrasonic homogeniser comprising cooling tank (100) for containing mixtures of step (C), connecting with progressive cavity pump (200) with cooling system (300) controlling pressure by pressure gauge before into the flow cell (400) with ultrasonic source (500) with frequency 20-40 kHz, amplitude 50-100%, and energy 2 kW, and collecting the mixtures of liquid matrix with graphene in cooling tank (600)15. The bulletproof plate as claimed in claim 2, wherein the polymer sheet with embedded graphene (001) is prepared from the step comprising:(A)Immerging polymer fibre from claims 3 and 4 into 5-15% by weight of the mixtures from claim 14.(B) Controlling the tensile force of the polymer fibre overall the system.(C) Extruding the polymer fibre by using extrusion force of 1-5 mPa, and temperature of 46-65 degree Celsius.(D) Cooling at 25-35 degree Celsius, and graphene is embedded in the polymer sheet with one-direction fibre.

16. The bulletproof plate as claimed in claim 1, wherein polymer sheet with embedded graphene (001) co-extruded with polymer sheet without embedded graphene (002) is prepared by the extrusion process comprising the steps of:(A) Stacking at least 2 polymer sheets or more with embedded graphene (001) from claim 15, having 0 / 90 degree of fibre in longitudinal and vertical direction.(B) Stacking at least 2 polymer sheets or more without embedded graphene (002), having 0 / 90 degree of fibre in longitudinal and vertical direction.(C) Stacking polymer from step (A) overlapping to polymer from step (B), polymer from step (A) is provided on outer radius curve.(D) Extruding polymer from step (C) with temperature of 120-140 degree Celsius, extrusion force of 5-15 mPa, 10-30 minutes, the temperature is set to upper mold, lower mold, or a combination thereof.(E) Cooling the extruded polymer sheet from step (D)17. The bulletproof plate as claimed in claim 1, wherein the composite structure with embedded graphene is prepared from the step comprising:(A) Partitioning the edge of extruded polymer from claim 16 with foam (003) with 6- 10 mm. thickness and 15-25 mm. width, and attaching with glue.(B) Attaching honeycomb fabric (004) having 1-2 mm. thickness onto material of step (A) by glue within foam edge.(C) Attaching ceramic plate (005) onto material of step (B) by glue.(D) Covering with a single or double weave fabric (006).(E) Molding composite structure from step (D) via vacuum infusion mold in closed system, matrix liquid is flowed under vacuum condition.(F) Hardening the composite of step (E) in mold under vacuum condition.

18. The bulletproof plate as claimed in claim 1, wherein foam (003) is selected from rubber foam, polyvinyl chloride foam with plasticizer, polyurethane foam, polyolefin foam, polystyrene foam, polycarbonate foam, polyphenolic foam, polyethylene foam, or a combination thereof, with 6-10 mm. thickness, and 15- 25 mm. width.

19. The bulletproof plate as claimed in claim 1, wherein honeycomb fabric (004) is polyester, Soric®, or a combination thereof, with 1-2 mm. thickness.

20. The bulletproof plate as claimed in claim 19, wherein honeycomb fabric (004) is Soric®.

21. The bulletproof plate as claimed in claim 1, wherein ceramic plate (005) is selected from silicon carbide, boron carbide, or a combination thereof.

22. The bulletproof plate as claimed in claim 1, wherein ceramic plate (005) is rectangle shape with 25-50 mm. width, 40-50 mm. length, and 6-10 mm. thickness.

23. The bulletproof plate as claimed in claim 1, wherein ceramic plate (005) is triangle shape with a base and height of 40-50 mm., and 6-10 mm. thickness.

24. The bulletproof plate as claimed in claim 1, wherein the single or double weave fabric (006) is selected from carbon fibre, glass fibre, aramid, or a combination thereof, with 160- 240 g / m2.

25. The bulletproof plate as claimed in claim 24, wherein the single or double weave fabric (006) is carbon fibre.

26. The bulletproof plate as claimed in claim 1, wherein the composite structure is prepared by vacuum infusion mold in closed system.

27. The bulletproof plate as claimed in claim 1, wherein the composite structure is prepared by mold, the lower mold is polymer reinforced fiberglass with 15-25 mm. of hole deepness, and 15-20 mm. of center of curve height.

28. The bulletproof plate as claimed in claim 1, wherein the composite structure is prepared by mold, the upper mold is silicon.

29. The bulletproof plate as claimed in claim 1, wherein the composite structure has matrix liquid flow under vacuum condition for 10-20 minutes.

30. The bulletproof plate as claimed in claim 1, wherein the composite structure has matrix liquid, the liquid matrix is thermosetting polymer selected from polyurethane resin, phenolic resin, urea formaldehyde resin, melamine formaldehyde resin, polyester resin, epoxy resin, epoxy resin mixing with graphene, or a combination thereof.

31. The bulletproof plate as claimed in claim 30, wherein the composite structure has matrix liquid, the liquid matrix is epoxy resin, or epoxy resin mixing with graphene.

32. The bulletproof plate as claimed in claim 30, wherein the composite structure is extruded via extrusion force under vacuum condition for 3-8 hours.

33. The bulletproof plate as claimed in claim 30, wherein the composite structure is hardening via extrusion force under vacuum condition for 3-8 hours.

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