CN100567606C - The application of CNT in northylen composite welfless cloth - Google Patents
The application of CNT in northylen composite welfless cloth Download PDFInfo
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- CN100567606C CN100567606C CNB2007100377192A CN200710037719A CN100567606C CN 100567606 C CN100567606 C CN 100567606C CN B2007100377192 A CNB2007100377192 A CN B2007100377192A CN 200710037719 A CN200710037719 A CN 200710037719A CN 100567606 C CN100567606 C CN 100567606C
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Abstract
The present invention relates to the application of CNT in northylen composite welfless cloth, nano particle is the two-dimensional nano CNT, the seamless hollow tube that surrounds by the former sub-grid of hexagonal carbon, two ends are covered by hemispheric big fullerene molecule, diameter be zero point several nanometers to tens nanometers, length is several to hundreds of micron.Preparation comprises: the pre-treatment of (1) CNT: the purifying and the processing that organises; With 1-4g CNT/ml and 0.01-0.04g/ml titanate coupling agent in organic solvent backflow 1-3 hour; (2) CNT is mixed with adhesive, stir 1-2h, vacuum defoamation at 60-80 ℃; (3) will strengthen body UHMWPE fiber uniform spreading on up-coiler; (4) gluing, gluing number of times are 1-2 time, in 40-70 ℃ of drying; (5) dry dry 10-20min behind the gluing down at 60 ± 3 ℃.The present invention makes the northylen composite welfless cloth serviceability temperature improve 10 ℃, and impact resistance improves 20%, has good heat resistance, intensity and creep resistance, energy shock resistance, shellproof, anti-lancination.
Description
Technical field
The invention belongs to the nano-textile Application Areas, particularly relate to the application of CNT in polyethylene (UHMWPE) composite welfless cloth.
Background technology
Polyethylene (UHMWPE) composite welfless cloth be by the UHMWPE fiber by even, parallel, straight and upright arrangement after, it is carried out making after gluing, the drying, US4,916,000 and US5,149,391 have described this process.Wherein the adhesive of gluing generally comprises polyethylene, crosslinked polyethylene, polypropylene, ethylenic copolymer, propylene copolymer, ethylene-propylene copolymer and other olefin polymers and copolymer, the resin that also has unsaturated polyester (UP), polybutadiene, polyisoprene, natural rubber, epoxy resin, poly-imines or the like many low modulus, in addition, also have EVA, EEA, SBS, SIS, TPR, SEBS etc. and fourth sodium glue, these thermoplasticity high-ductility glues of butadiene-styrene rubber PVB, PVA or the like.The elastomer of these low modulus is coated on each root fiber, except fixing as the fiber that strengthens body, can also improve shellproof, the anti-stab performance of shock resistance of composite.To this, in those early years existing US 4,403,012 patent, nearly 2 years US6,825,137 and CN 1278566 patents on report is also arranged.
Yet this compound no latitude cloth, because shortcoming as the adhesive self of matrix, make the combination property of compound no latitude cloth be affected, be embodied in poor heat resistance, comprehensive mechanical intensity is also relatively poor, and creep is serious, by its UHMWPE composite welfless cloth of making, the impulsive force of " passivation " bullet can only reach bulletproof effect by increasing the no latitude cloth number of plies effectively, but can cause the general load as soldier, police of increase so again.Therefore, how to change the heat resistance of UHMWPE composite welfless cloth, make it have higher impact resistance, effectively the impulsive force of " passivation " bullet has become shellproof inexorable trend of protecting product research.
Summary of the invention
The technical problem that will solve required for the present invention provides the application of CNT in northylen composite welfless cloth, improves shellproof, the anti-stab performance of its shock resistance.
The application of CNT of the present invention in northylen composite welfless cloth, CNT have two-dimentional yardstick to be in nanoscale in the space.
Described CNT is the seamless hollow tube that is surrounded by the former sub-grid of hexagonal carbon, and two ends are covered by hemispheric big fullerene molecule, diameter be zero point several nanometers to tens nanometers, length is several to hundreds of micron.
Described preparation method of carbon nano-tube comprises the steps:
(1) pre-treatment of CNT, the purifying of a. CNT:
CNT be impregnated in the mixed solution of sulfuric acid and potassium permanganate, and the concentration of potassium permanganate in sulfuric acid is 1-8g/100ml, handles 1-5 hour under reflux temperature, and the impurity on CNT (carbon nano-tube) surface is removed in oxidation, through cleaning, obtains the carbon pipe behind the purifying;
B. the processing that organises of CNT:
With the 1-4g CNT/ml behind the purifying and 0.01-0.04g/ml titanate coupling agent in organic solvent backflow 1-3 hour, obtain the carbon pipe after the coupling agent grafting;
(2) CNT is mixed with adhesive, stir 1-2h, vacuum defoamation at 60-80 ℃;
(3) will strengthen body UHMWPE fiber uniform spreading on up-coiler;
(4) gluing, gluing number of times are 1-2 time, in 40-70 ℃ of drying;
(5) dry down at 60 ± 3 ℃ behind the gluing, dry 10-20min can make.
It is 1-3g CNT/100ml. that the concentration of described potassium permanganate in sulfuric acid is preferably treating capacity
Described organic solvent is ethanol, isopropyl alcohol or propyl alcohol,
Described titanate coupling agent is C
1-C
4Titanate esters, as butyl titanate or metatitanic acid methyl esters,
Described adhesive is the mixed solvent type adhesive of polystyrene triblock copolymer body or hydrogenated polystyrene triblock copolymer body; Comparatively ideally be: KRATON D-1107, KRATON D-1161, KRATON G-1650 etc.The solvent of this adhesive is that solubility parameter is a volatile solvent between the 8.0-8.5, as: benzene, toluene; Chloroform, carbon tetrachloride; The sixth of the twelve Earthly Branches alkane, ring the sixth of the twelve Earthly Branches alkane, chlorination ring alkane in the sixth of the twelve Earthly Branches; Diethyl ether, methyl-isobutyl ether etc. different solvents is slightly variant to the soft or hard section dissolving of block copolymer, the solvent of solvent polymerization body is good with mixed solvent. the part by weight of adhesive and solvent is 10-40%: 90-60%, and the weight ratio of mixed solvent is an alkane: ethers: ester class=3-10: 0.1-0.5: 1.
The UHMWPE composite welfless cloth is a kind ofly to be composited by UHMWPE fiber and adhesive, in order to improve the shellproof drag of material better, improve the heat resistance of UHMWPE fiber, in adhesive, add nano material, the present invention be chosen in have two-dimentional yardstick to be in nanoscale in the space CNT as the filler in the adhesive, with carbon nano-tube filled in matrix material, in order to improve the anti-anti-impact force of shellproof composite fibre, the impact of passivation bullet, cutter.
The strength ratio steel of CNT is high more than 100 times, and Young's modulus is up to 1TPa, and proportion has only 1/6 of steel, and CNT also has high toughness simultaneously, and is very soft, is reinforcement material fabulous in the composite.CNT can keep nanoscale on the bidimensional yardstick, because the acting in conjunction of hollow nano pipe and helicity has determined that it is a kind of perfect, the thinnest fibrous material, the intrinsic property that had both had carbon fiber has the electrical and thermal conductivity of metal material, the heat-proof corrosion-resistant of ceramic material, the softness property compiled of textile fabric and the workability of macromolecular material again.
CNT is except having very excellent physical property, outside high intensity, modulus, owing to be the big L/D ratio structure, and can dispersive stress, the passivation impulsive force.The interpolation of CNT makes molecule with the form mass motion of fritter, and except reducing macromolecular creep, the resistance that is subjected to is just bigger.In addition, add CNT and can improve heat resistance, be that physical crosslinking select and the effect of nucleator because CNT can play, make adhesive or polyethylene molecule be attached on it or along CNT wall oriented crystalline, formation is to the obstruction of cutter, bullet.
The present invention adds nano materials such as CNT in the adhesive that compound no latitude measuring fiber is used, not only improved the mechanical performance of host material adhesive, also changed simultaneously the heat endurance of material, improved the heat resistance of UHMWPE composite welfless cloth, make its serviceability temperature improve 10 ℃, impact resistance improves about 20%.
Evidence, UHMWPE composite welfless cloth of the present invention can overcome the defective that prior art exists to a great extent, obtain the anti-good bulletproof composite fiber of shock resistance, because CNT has a lot of premium properties, it has good heat resistance, intensity and creep resistance, so, can reach the heat resistance and the creep resistance that improve the UHMWPE fiber theoretically, thereby effective impulsive force of passivation bullet according to the shock resistance principle of composite.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
The 2g CNT be impregnated in the mixed solution of 100ml sulfuric acid and potassium permanganate, handled 1.5 hours under reflux temperature, the concentration of potassium permanganate in sulfuric acid is 5g/100ml; CNT behind the 2g purifying and butyl titanate coupling agent were refluxed in ethanol 2 hours, obtain the CNT after the coupling agent grafting, the concentration of titanate coupling agent is 0.03g/ml in the ethanol.
Certain quantity of carbon nanometer pipe is mixed with adhesive, stir 1-2h, vacuum defoamation at 60-80 ℃.To strengthen body UHMWPE fiber wound in parallel on up-coiler, afterwards gluing on the UHMWPE fiber (or with in UHMWPE fiber immersion adhesive).The gluing number of times is 1-2 time, notices that gluing will be evenly.The adhesive that present embodiment adopts is KRATON G-1650, be dissolved in mixed solvent (hexane: diethyl ether: ethyl acetate=5: 0.5: 1 by weight 15%, add antioxidant again), even behind the gluing with the spreading knife gluing, place 60 ℃ of oven dry of baking oven, solidify, oven temperature is 60 ± 3 ℃, is about 20min drying time.It is compound that the composite of above-mentioned gained is carried out quadrature.They can be two layers staggered, also can be four layers staggered, resulting product structure is corresponding to be [0 °/90 °] or [0 °/90 °]
2(incorporation of CNT is 4.6g/m
2No latitude cloth)
Bulletproof effect: with 40 layers, 450mm * 450mm AD=160g/m
2It is on the target holder of clay that the neat stack of UD material places backing, adopts 51 formula balls, by the 662EV of U.S. army
50Test standard records V with 51 formula Long Barrels, 51 formula balls (lead for retractable pencil bullet)
50〉=612m/s.
Embodiment 2
Except the incorporation of CNT is 2g/m
2Outside the no latitude cloth, other are all identical with embodiment 1, make compound no latitude cloth.
Bulletproof effect: with 40 layers, 450mm * 450mm AD=160g/m
2It is on the target holder of clay that the neat stack of UD material places backing, adopts 51 formula balls, by the 662EV of U.S. army
50Test standard records V with 51 formula Long Barrels, 51 formula balls (lead for retractable pencil bullet)
50〉=557m/s.
Embodiment 3
Except not adding CNT, and a certain amount of organo montmorillonite is mixed with adhesive, mixed proportion is 1: 19, stirs 1-2h at 60-80 ℃, and outside the vacuum defoamation, other are all identical with embodiment 1, make compound no latitude cloth.The imvite incorporation is 4.6g/m
2No latitude cloth.
Bulletproof effect: with 40 layers, 450mm * 450mm AD=160g/m
2It is on the target holder of clay that the neat stack of UD material places backing, adopts 51 formula balls, by the 662EV of U.S. army
50Test standard records V with 51 formula Long Barrels, 51 formula balls (lead for retractable pencil bullet)
50〉=580m/s.
Embodiment 4
Except the incorporation of organo montmorillonite is 2g/m
2Outside the no latitude cloth, it is all identical with embodiment 3, makes compound no latitude cloth.
Bulletproof effect: with 40 layers, 450mm * 450mm AD=160g/m
2It is on the target holder of clay that the neat stack of UD material places backing, adopts 51 formula balls, by the 662EV of U.S. army
50Test standard records V with 51 formula Long Barrels, 51 formula balls (lead for retractable pencil bullet)
50〉=538m/s.
Embodiment 5
Except not adding CNT, and a certain amount of graphite powder is mixed with adhesive, mixed proportion is 1: 19, stirs 1-2h at 60-80 ℃, and outside the vacuum defoamation, other are all identical with embodiment 1, make compound no latitude cloth.The graphite powder incorporation is 4.6g/m
2No latitude cloth.
Bulletproof effect: with 40 layers, 450mm * 450mm AD=160g/m
2It is on the target holder of clay that the neat stack of UD material places backing, adopts 51 formula balls, by the 662EV of U.S. army
50Test standard records V with 51 formula Long Barrels, 51 formula balls (lead for retractable pencil bullet)
50〉=584m/s.
Embodiment 6
Except the incorporation of graphite powder is 2g/m
2Outside the no latitude cloth, other are all identical with embodiment 3, make compound no latitude cloth.
Bulletproof effect: with 40 layers, 450mm * 450mm AD=160g/m
2It is on the target holder of clay that the neat stack of UD material places backing, adopts 51 formula balls, by the 662EV of U.S. army
50Test standard records V with 51 formula Long Barrels, 51 formula balls (lead for retractable pencil bullet)
50〉=540m/s.
Comparative example
Except not adding any additives, other are all identical with experimental example 1.
Bulletproof effect: with 40 layers, 450mm * 450mm AD=160g/m
2It is on the target holder of clay that the neat stack of UD material places backing, adopts 51 formula balls, by the 662EV of U.S. army
50Test standard records V with 51 formula Long Barrels, 51 formula balls (lead for retractable pencil bullet)
50〉=525m/s.
Claims (10)
1. the application of CNT in northylen composite welfless cloth, described CNT have two-dimentional yardstick to be in nanoscale in the space.
2. the application of CNT according to claim 1 in northylen composite welfless cloth, described CNT is the seamless hollow tube that is surrounded by the former sub-grid of hexagonal carbon, two ends are covered by hemispheric big fullerene molecule, diameter be zero point several nanometers to tens nanometers, length is several to hundreds of micron.
3. the application of CNT according to claim 1 in northylen composite welfless cloth, described preparation method comprises the steps:
(1) pre-treatment of CNT
A. the purifying of CNT:
CNT be impregnated in the mixed solution of sulfuric acid and potassium permanganate, and the concentration of potassium permanganate in sulfuric acid is 1-8g/100ml, and reflux temperature was handled 1-5 hour down, and surface impurity is removed in oxidation, cleans the carbon pipe that obtains behind the purifying;
B. the processing that organises of CNT:
With above-mentioned 1-4g CNT/ml and 0.01-0.04g/ml titanate coupling agent in organic solvent backflow 1-3 hour, obtain the carbon pipe after the coupling agent grafting;
(2) above-mentioned CNT is mixed with adhesive, stir 1-2h, vacuum defoamation at 60-80 ℃;
(3) will strengthen body polyethylene (UHMWPE) fiber uniform spreading;
(4) gluing is 1-2 time, 40-70 ℃ of drying;
(5) dry down at 60 ± 3 ℃ behind the gluing, dry 10-20min promptly makes.
4. the application of CNT according to claim 3 in northylen composite welfless cloth is characterized in that: the concentration of potassium permanganate in sulfuric acid of described step (1) is 1-3g CNT/100ml.
5. the application of CNT according to claim 3 in northylen composite welfless cloth is characterized in that: the organic solvent of described step (1) is ethanol, isopropyl alcohol or propyl alcohol.
6. the application of CNT according to claim 3 in northylen composite welfless cloth is characterized in that: the titanate coupling agent of described step (1) is C
1-C
4Titanate esters.
7. the application of CNT according to claim 6 in northylen composite welfless cloth is characterized in that: the titanate coupling agent of described step (1) is butyl titanate or metatitanic acid methyl esters.
8. the application of CNT according to claim 3 in northylen composite welfless cloth is characterized in that: the adhesive of described step (2) is the intermixture of polystyrene triblock copolymer body or hydrogenated polystyrene triblock copolymer body.
9. the application of CNT according to claim 8 in northylen composite welfless cloth is characterized in that: the solvent of described step (2) intermixture is selected from benzene, toluene, chloroform, carbon tetrachloride; Hexane, cyclohexane, chlorination cyclohexane; Diethyl ether, methyl-isobutyl ether, the weight ratio of mixed solvent are alkane: ethers: ester class=3-10: 0.1-0.5: 1.
10. according to Claim 8 or 9 application of described CNT in northylen composite welfless cloth, it is characterized in that: the weight ratio of adhesive and solvent is 10-40%: 90-60%.
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