CN109808266B - Amorphous alloy composite bulletproof material and preparation method thereof - Google Patents
Amorphous alloy composite bulletproof material and preparation method thereof Download PDFInfo
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- CN109808266B CN109808266B CN201910016429.2A CN201910016429A CN109808266B CN 109808266 B CN109808266 B CN 109808266B CN 201910016429 A CN201910016429 A CN 201910016429A CN 109808266 B CN109808266 B CN 109808266B
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Abstract
The invention discloses an amorphous alloy composite bulletproof material and a preparation method thereof. The amorphous alloy composite bulletproof material is prepared by taking amorphous alloy material particles, ultra-high molecular weight polyethylene fibers, waterborne polyurethane, polyolefin resin, titanium boride powder and a carbon nanotube film as raw materials. The polyolefin resin and the ultrahigh molecular weight polyethylene fiber have good interface effect, can improve the binding force of the solid particle raw material on the surface of the carbon nano tube film, and simultaneously, the ultrahigh molecular weight polyethylene fiber as a supporting structure can enhance the stability of the composite bulletproof material and prolong the service life of the bulletproof material. The amorphous alloy material can enhance the bulletproof performance and improve the flexibility and the processing performance of the bulletproof material. The amorphous alloy composite bulletproof material which is light in weight, good in bulletproof performance and good in processing performance is prepared by selecting proper raw materials and proportion.
Description
Technical Field
The invention belongs to the field of protective materials, and particularly relates to an amorphous alloy composite bulletproof material and a preparation method thereof.
Background
While the scientific and technical level and the economic level are continuously developed, terrorist events occur in the global scope, and the present terrorist events have the characteristics of large lethality, wide injury range and rapid injury death, wherein the main injuries are from penetration of firearms and ammunition and striking of explosive fragments. In order to reduce casualties caused by terrorist events, the research and development of bulletproof materials are paid more and more attention, and the application fields of the bulletproof materials are wider and wider, such as small-sized protective equipment like bulletproof clothes and bulletproof helmets, and large-sized weapon equipment like automobiles, airplanes, tanks and ships.
The high-performance bulletproof material absorbs and disperses kinetic energy through deformation of the fibers, so that bullets or explosive fragments flying at high speed are retarded and become cake-shaped or mushroom-shaped, and the bulletproof effect is achieved through damping and buffering of the bulletproof material. The existing bulletproof materials which are used more often comprise Kevlar fibers, ultrahigh molecular weight polyethylene fibers (UHMWPE), glass fibers, ceramic materials, steel plates, acrylic plate composite materials and the like, wherein the Kevlar fibers are low in density, high in strength, good in toughness, good in thermal stability, easy to machine and form, high in strength which is more than 5 times that of steel with the same mass, and only one fifth of that of the steel, and widely applied to bulletproof and stab-resistant equipment, but the Kevlar fibers are high in price per se, high in industrial use cost and limited in use of the Kevlar fibers. The strength and the modulus of UHMWPE fibers are higher than those of Kevlar fibers, the density is lower, the ballistic protection performance of the UHMWPE fibers exceeds that of aromatic polyamide fibers represented by Kevlar fibers, the breaking elongation is higher than that of high-strength carbon fibers, and the UHMWPE fibers are bulletproof materials with excellent performance.
The bulletproof material is the basis for preparing bulletproof equipment, develops a new bulletproof material, meets the bulletproof requirement, simultaneously enhances the processing performance and the forming performance of the bulletproof material, and has important significance for developing the bulletproof equipment and protecting the life safety of personnel on duty.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides an amorphous alloy composite bulletproof material and a preparation method thereof. The amorphous alloy composite bulletproof material is prepared by taking amorphous alloy material particles, ultra-high molecular weight polyethylene fibers, waterborne polyurethane, polyolefin resin, titanium boride powder and a carbon nanotube film as raw materials. The polyolefin resin and the ultrahigh molecular weight polyethylene fiber have good interface effect, can improve the binding force of solid particle raw materials on the surface of the carbon nano tube film, simultaneously, the ultrahigh molecular weight polyethylene fiber as a supporting structure can enhance the stability of the composite bulletproof material, and when bullets or explosive fragments are penetrated, the deformation of the bulletproof material is reduced, and the service life of the bulletproof material is prolonged. The amorphous alloy material can enhance the bulletproof performance and improve the flexibility and the processing performance of the bulletproof material. The amorphous alloy composite bulletproof material has the advantages of light weight, good bulletproof performance and good processing performance.
The technical effect to be achieved by the invention is realized by the following scheme:
the invention provides an amorphous alloy composite bulletproof material, which comprises the following components in parts by mass:
amorphous alloy material particles: 32 to 50 portions of
Ultra-high molecular weight polyethylene fiber: 6-12 parts of
Aqueous polyurethane: 20-30 parts of
Polyolefin resin: 18-32 parts of
Titanium boride powder: 8-15 parts of
Carbon nanotube film: 12 to 25 portions of
The molecular weight of the ultra-high molecular weight polyethylene fiber is 2 multiplied by 106~4×106。
The amorphous alloy composite bulletproof material is prepared by taking amorphous alloy material particles, ultra-high molecular weight polyethylene fibers, waterborne polyurethane, polyolefin resin, titanium boride powder and a carbon nanotube film as raw materials. The carbon nano tube has a high energy absorption characteristic in self structure and is formed by carbon atoms sp2When the carbon nano tube is impacted in the carbon nano tube film, stress waves can be rapidly transmitted to enable more carbon nano tubes to participate in energy absorption, so that the kinetic energy of bullets or fragments can be rapidly absorbed, and the bulletproof effect is achieved. The titanium boride powder is a hexagonal system, and a covalent bond and an ionic bond exist in the structure at the same time, so that the titanium boride powder has the characteristics of high hardness, high melting point, wear resistance, corrosion resistance and excellent chemical stabilityDirectly improves the penetration resistance of the bulletproof material. However, titanium boride powder and carbon nanotube films have stable properties, have poor binding force with other solid particles and resin materials in the bulletproof material, have poor processing capability, and are difficult to prepare bulletproof materials with excellent performance and easy processing.
The amorphous alloy material has high activity, has good binding force with polyolefin resin, titanium boride powder and carbon nanotube film, can form a uniform dispersion system in waterborne polyurethane, and can be used for preparing a bulletproof material with excellent performance. Meanwhile, the amorphous alloy material has an amorphous structure, and when the amorphous alloy material is acted with the ultra-high molecular weight polyethylene fiber and the carbon nanotube film together, the action time of bullets or explosive fragments and the bulletproof material can be prolonged, the buffering effect is enhanced, and the impact force of the bullets or the explosive fragments on the bulletproof material is dispersed; when the bulletproof material is hit, the bulletproof material is prevented from losing the bulletproof effect due to the fact that the bulletproof material breaks along the edge of the crystalline structure of the material. Namely, the amorphous alloy material can enhance the flexibility and the processing performance of the bulletproof material while enhancing the bulletproof performance.
The polyolefin resin and the ultra-high molecular weight polyethylene fiber have good interface effect, can improve the binding force of solid particle raw materials on the surface of the carbon nano tube film, and meanwhile, the ultra-high molecular weight polyethylene fiber as a supporting structure can enhance the stability of the composite bulletproof material, so that when bullets or explosive fragments are penetrated, the deformation of the bulletproof material is reduced, and the service life of the bulletproof material is prolonged.
Further, the amorphous alloy material particles are one or more of zirconium-based amorphous alloy material particles, copper-based amorphous alloy material particles and cobalt-based amorphous alloy material particles.
Further, the grain diameter of the amorphous alloy material grains is 15-50 μm.
Further, the diameter of the ultra-high molecular weight polyethylene fiber is 15-30 μm; the thickness of the carbon nano tube film is 5-10 mu m.
Further, the preparation method of the polyolefin resin comprises the following steps: adding polyethylene into a dispersing agent at a stirring speed of 800-; the mass ratio of the polyethylene to the dispersing agent to the foaming agent to the flatting agent to the maleic anhydride to the benzoyl peroxide is 1: (0.5-0.8): (0.02-0.05): (0.03-0.07): (0.8-2.5): (0.08-0.1).
Further, the dispersing agent is one or more of polyethylene glycol, barium stearate, glyceryl stearate and paraffin; the foaming agent is one or more of methyl isobutyl carbinol, lauryl sodium sulfate and fatty alcohol-polyoxyethylene ether sodium sulfate; the leveling agent is polydimethylsiloxane.
Further, the titanium boride powder is prepared from titanium dioxide, boron carbide, carbon black, a binder and a sintering aid in a mass ratio of 1: (1.8-3.2): (0.8-1.5): (0.1-0.4): (0.03-0.06) mixing and grinding for 30-60min, and pressureless sintering at 1100-1500 ℃.
Further, the binder is a phenolic resin binder or a polyurethane binder; the sintering aid is one or more of calcium oxide, magnesium oxide and silicon dioxide.
The invention also provides a preparation method of the amorphous alloy composite bulletproof material, which comprises the following steps:
s01, arranging the ultra-high molecular weight polyethylene fibers on the surface of the carbon nanotube film to obtain the carbon nanotube film with a supporting structure;
s02, uniformly dispersing the amorphous alloy material particles, the polyolefin resin and the titanium boride powder in the waterborne polyurethane;
and S03, coating the uniformly dispersed mixture in the S02 on the surface of the carbon nanotube film with the support structure in the S01, and drying to obtain the amorphous alloy composite bulletproof material.
Further, the arrangement mode of the ultra-high molecular weight polyethylene fibers is one or more of UD arrangement, 2D woven fabric arrangement, 3D orthogonal woven fabric arrangement and 3D angle interlocking arrangement.
The invention has the following advantages:
1. the amorphous alloy bulletproof material has the advantages that the density of the raw materials for preparing the amorphous alloy bulletproof material is low, and the prepared bulletproof material is light in weight and easy to store and transport.
2. In the preparation process of the amorphous alloy bulletproof material, the amorphous alloy material, the titanium boride powder, the ultra-high molecular weight polyethylene fiber, the polyethylene resin and the carbon nanotube film interact with each other, so that the rigid impact of penetration of bullets or fragments can be reduced, the impact can be fully dispersed on the bulletproof material, and the bulletproof performance is good.
3. The solid particle raw material and the polyethylene resin raw material are dispersed in the waterborne polyurethane, so that the use amount of toxic and harmful organic solvents is small, and the environment-friendly effect is achieved.
4. The amorphous alloy bulletproof material has good flexibility, is easy to process, can be used as bulletproof clothes and bulletproof helmets, and has high wearing comfort; when the anti-bullet device is used as large-scale weapon equipment, the anti-bullet performance of the equipment can be effectively enhanced.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
1. Preparation of polyolefin resin:
adding polyethylene into polyethylene glycol at a stirring speed of 1000r/min, uniformly stirring, then sequentially adding methyl isobutyl carbinol and polydimethylsiloxane, continuously stirring for 30min, adjusting the stirring speed to 400r/min, adding maleic anhydride and benzoyl peroxide in a concurrent flow manner, stirring for 12min, adding the stirred mixture into a double-screw extruder, extruding, granulating and grinding to obtain a polyolefin resin with the particle size of 20-40 mu m; wherein the mass ratio of polyethylene, polyethylene glycol, methyl isobutyl carbinol, polydimethylsiloxane, maleic anhydride and benzoyl peroxide is 1: 0.5: 0.03: 0.05: 1.2: 0.08.
2. preparing titanium boride powder:
titanium dioxide, boron carbide, carbon black, phenolic resin binder and calcium oxide are mixed according to the mass ratio of 1: 2.1: 0.9: 0.2: 0.04, grinding for 35min, and sintering at 1200 deg.C under no pressure to obtain titanium boride powder.
3. Preparing the amorphous alloy composite bulletproof material:
s01, mixing the ultra-high molecular weight polyethylene fiber (molecular weight is 3 x 10)6The diameter is 25-30 mu m) is arranged on the surface of the carbon nano tube film (the thickness is 8 mu m) in a UD arrangement mode, and the carbon nano tube film with a support structure is prepared;
s02, uniformly dispersing zirconium-based amorphous alloy material particles (the particle size is 20-30 mu m), polyolefin resin and titanium boride powder in waterborne polyurethane;
and S03, coating the uniformly dispersed mixture in the S02 on the surface of the carbon nanotube film with the support structure in the S01, and drying to obtain the amorphous alloy composite bulletproof material.
In the embodiment, the mass parts of the zirconium-based amorphous alloy material particles, the ultrahigh molecular weight polyethylene fibers, the waterborne polyurethane, the polyolefin resin, the titanium boride powder and the carbon nanotube film are 40 parts, 6 parts, 21 parts, 20 parts, 10 parts and 15 parts respectively.
Example 2
1. Preparation of polyolefin resin:
adding polyethylene into paraffin wax at a stirring speed of 1000r/min, uniformly stirring, then sequentially adding sodium dodecyl sulfate and polydimethylsiloxane, continuously stirring for 30min, adjusting the stirring speed to 400r/min, adding maleic anhydride and benzoyl peroxide in a concurrent flow manner, stirring for 12min, adding the stirred mixture into a double-screw extruder, extruding, granulating and grinding to obtain a polyolefin resin with the particle size of 20-40 mu m; wherein the mass ratio of polyethylene, paraffin, sodium dodecyl sulfate, polydimethylsiloxane, maleic anhydride and benzoyl peroxide is 1: 0.6: 0.03: 0.03: 0.8: 0.08.
2. preparing titanium boride powder:
titanium dioxide, boron carbide, carbon black, phenolic resin binder and calcium oxide are mixed according to the mass ratio of 1: 2.1: 1.5: 0.3: 0.04, grinding for 35min, and sintering at 1200 deg.C under no pressure to obtain titanium boride powder.
3. Preparing the amorphous alloy composite bulletproof material:
s01, mixing the ultra-high molecular weight polyethylene fiber (molecular weight is 3 x 10)6Diameter of 25-30 μm) is arranged on the surface of the carbon nanotube film (thickness of 8 μm) in a 3D orthogonal woven fabric arrangement mode to prepare the carbon nanotube film with a supporting structure;
s02, uniformly dispersing copper-based amorphous alloy material particles (the particle size is 20-30 mu m), polyolefin resin and titanium boride powder in waterborne polyurethane;
and S03, coating the uniformly dispersed mixture in the S02 on the surface of the carbon nanotube film with the support structure in the S01, and drying to obtain the amorphous alloy composite bulletproof material.
In the embodiment, the mass parts of the copper-based amorphous alloy material particles, the ultrahigh molecular weight polyethylene fibers, the waterborne polyurethane, the polyolefin resin, the titanium boride powder and the carbon nanotube film are 40 parts, 10 parts, 21 parts, 20 parts, 8 parts and 15 parts respectively.
Example 3
1. Preparation of polyolefin resin:
adding polyethylene into polyethylene glycol at a stirring speed of 1000r/min, uniformly stirring, then sequentially adding methyl isobutyl carbinol and polydimethylsiloxane, continuously stirring for 30min, adjusting the stirring speed to 400r/min, adding maleic anhydride and benzoyl peroxide in a concurrent flow manner, stirring for 12min, adding the stirred mixture into a double-screw extruder, extruding, granulating and grinding to obtain a polyolefin resin with the particle size of 20-40 mu m; wherein the mass ratio of polyethylene, polyethylene glycol, methyl isobutyl carbinol, polydimethylsiloxane, maleic anhydride and benzoyl peroxide is 1: 0.8: 0.05: 0.03: 0.8: 0.08.
2. preparing titanium boride powder:
titanium dioxide, boron carbide, carbon black, phenolic resin binder and calcium oxide are mixed according to the mass ratio of 1: 1.8: 1.2: 0.3: 0.05 mixing, grinding for 35min, and pressureless sintering at 1200 deg.C to obtain titanium boride powder.
3. Preparing the amorphous alloy composite bulletproof material:
s01, mixing the ultra-high molecular weight polyethylene fiber (molecular weight is 3 x 10)6The diameter is 25-30 mu m) is arranged on the surface of the carbon nano tube film (the thickness is 8 mu m) in a 2D woven fabric arrangement mode, and the carbon nano tube film with a supporting structure is prepared;
s02, uniformly dispersing zirconium-based amorphous alloy material particles (the particle size is 20-30 mu m), polyolefin resin and titanium boride powder in waterborne polyurethane;
and S03, coating the uniformly dispersed mixture in the S02 on the surface of the carbon nanotube film with the support structure in the S01, and drying to obtain the amorphous alloy composite bulletproof material.
In the embodiment, the mass parts of the zirconium-based amorphous alloy material particles, the ultrahigh molecular weight polyethylene fibers, the waterborne polyurethane, the polyolefin resin, the titanium boride powder and the carbon nanotube film are 32 parts, 10 parts, 25 parts, 20 parts, 8 parts and 15 parts respectively.
Examples 4 to 10
Compared with the embodiment 1, the difference of the embodiments 4 to 10 is that the compositions of the raw materials in the polyolefin resin, the titanium boride powder and the amorphous alloy composite bulletproof material are the same, and the mixture ratio of the compositions is different.
The compositions and mass ratios of the polyolefin resins in examples 1 to 10 are as follows:
the composition and mass ratio of the titanium boride powder in examples 1 to 10 are as follows:
the compositions and the parts by weight of the amorphous alloy composite bulletproof material in the examples 1 to 10 are as follows:
the amorphous alloy composite bulletproof materials in examples 1 to 10 were tested for bulletproof performance by ballistic v of the amorphous alloy composite bulletproof materials in examples 1 to 1050Test, v50The average velocity of the bullet at a penetration probability of 50%. The test results are shown in the following table:
the test results in the table show that the amorphous alloy composite bulletproof material has good bulletproof performance.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the embodiments of the present invention and not for limiting the same, and although the embodiments of the present invention are described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the embodiments of the present invention, and these modifications or equivalent substitutions cannot make the modified technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (5)
1. An amorphous alloy composite bulletproof material is characterized in that: the composition comprises the following components in parts by mass:
amorphous alloy material particles: 32 to 50 portions of
Ultra-high molecular weight polyethylene fiber: 6-12 parts of
Aqueous polyurethane: 20-30 parts of
Polyolefin resin: 18-32 parts of
Titanium boride powder: 8-15 parts of
Carbon nanotube film: 12 to 25 portions of
The molecular weight of the ultra-high molecular weight polyethylene fiber is 2 multiplied by 106～4×106；
The preparation method of the polyolefin resin comprises the following steps: adding polyethylene into a dispersing agent at a stirring speed of 800-; the mass ratio of the polyethylene to the dispersing agent to the foaming agent to the flatting agent to the maleic anhydride to the benzoyl peroxide is 1: (0.5-0.8): (0.02-0.05): (0.03-0.07): (0.8-2.5): (0.08-0.1);
the titanium boride powder is prepared from titanium dioxide, boron carbide, carbon black, a binder and a sintering aid in a mass ratio of 1: (1.8-3.2): (0.8-1.5): (0.1-0.4): (0.03-0.06), grinding for 30-60min, and sintering under no pressure at the temperature of 1100-1500 ℃;
the dispersant is one or more of polyethylene glycol, barium stearate, glyceryl stearate and paraffin; the foaming agent is one or more of methyl isobutyl carbinol, lauryl sodium sulfate and fatty alcohol-polyoxyethylene ether sodium sulfate; the flatting agent is polydimethylsiloxane;
the preparation method of the amorphous alloy composite bulletproof material comprises the following steps:
s01, arranging the ultra-high molecular weight polyethylene fibers on the surface of the carbon nanotube film to obtain the carbon nanotube film with a supporting structure;
s02, uniformly dispersing the amorphous alloy material particles, the polyolefin resin and the titanium boride powder in the waterborne polyurethane;
s03, coating the uniformly dispersed mixture in the S02 on the surface of the carbon nanotube film with the support structure in the S01, and drying to obtain the amorphous alloy composite bulletproof material;
the arrangement mode of the ultra-high molecular weight polyethylene fibers is one or more of UD arrangement, 2D woven fabric arrangement, 3D orthogonal woven fabric arrangement and 3D angle interlocking arrangement.
2. The amorphous alloy composite ballistic resistant material of claim 1 wherein: the amorphous alloy material particles are one or more of zirconium-based amorphous alloy material particles, copper-based amorphous alloy material particles and cobalt-based amorphous alloy material particles.
3. The amorphous alloy composite ballistic resistant material of claim 1 wherein: the grain diameter of the amorphous alloy material particles is 15-50 μm.
4. The amorphous alloy composite ballistic resistant material of claim 1 wherein: the diameter of the ultra-high molecular weight polyethylene fiber is 15-30 μm; the thickness of the carbon nano tube film is 5-10 mu m.
5. The amorphous alloy composite ballistic resistant material of claim 1 wherein: the binder is phenolic resin binder or polyurethane binder; the sintering aid is one or more of calcium oxide, magnesium oxide and silicon dioxide.
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| JPS6229899A (en) * | 1985-07-30 | 1987-02-07 | 小林 正巳 | Bulletproof material |
| CN101450982B (en) * | 2007-11-29 | 2011-04-27 | 维龙(上海)新材料科技有限公司 | Couple method of polyolefin molecular chain |
| CN101555140B (en) * | 2009-05-22 | 2011-10-26 | 东北大学 | Loose sintering preparation method of titanium diboride compact complex material |
| KR101860590B1 (en) * | 2010-11-02 | 2018-05-23 | 더 나노스틸 컴퍼니, 인코포레이티드 | Glassy Nano-Materials |
| CN104944432B (en) * | 2015-06-30 | 2017-11-03 | 莱芜亚赛陶瓷技术有限公司 | A kind of ultra-fine richness10B titanium diboride powders and preparation method thereof |
| CN205272786U (en) * | 2015-11-12 | 2016-06-01 | 河北安泰富源安全设备制造有限公司 | Sheet is prevented stinging by nonmetal |
| CN105547051A (en) * | 2015-12-12 | 2016-05-04 | 西安交通大学 | Metal glass enhanced gradient-density armored protection device |
| CN107024146B (en) * | 2016-01-29 | 2019-07-26 | 深圳前海量子翼纳米碳科技有限公司 | Carbon nanotube agglomerate is in preparing purposes and its preparation method in ballistic composite |
| CN107523209B (en) * | 2017-09-26 | 2020-06-05 | 河南青山环保科技有限公司 | Water-based amorphous alloy anticorrosive paint and preparation method thereof |
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