CN112391691B - Bulletproof material prepared from ultra-high molecular weight polyethylene/shear thickening fluid composite fiber - Google Patents
Bulletproof material prepared from ultra-high molecular weight polyethylene/shear thickening fluid composite fiber Download PDFInfo
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- CN112391691B CN112391691B CN202010997239.6A CN202010997239A CN112391691B CN 112391691 B CN112391691 B CN 112391691B CN 202010997239 A CN202010997239 A CN 202010997239A CN 112391691 B CN112391691 B CN 112391691B
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- weight polyethylene
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- 239000004699 Ultra-high molecular weight polyethylene Substances 0.000 title claims abstract description 86
- 229920000785 ultra high molecular weight polyethylene Polymers 0.000 title claims abstract description 86
- 239000000835 fiber Substances 0.000 title claims abstract description 81
- 230000008719 thickening Effects 0.000 title claims abstract description 69
- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 239000012530 fluid Substances 0.000 title claims abstract description 61
- 239000000463 material Substances 0.000 title claims abstract description 50
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- 238000001035 drying Methods 0.000 claims abstract description 11
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- 238000009940 knitting Methods 0.000 claims abstract description 7
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- 238000009941 weaving Methods 0.000 claims abstract 6
- 238000002156 mixing Methods 0.000 claims description 21
- 239000003292 glue Substances 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 15
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 14
- 239000002612 dispersion medium Substances 0.000 claims description 14
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000003921 oil Substances 0.000 claims description 10
- 235000019198 oils Nutrition 0.000 claims description 10
- 239000004215 Carbon black (E152) Substances 0.000 claims description 9
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 9
- 229930195733 hydrocarbon Natural products 0.000 claims description 9
- 150000002430 hydrocarbons Chemical class 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 239000002480 mineral oil Substances 0.000 claims description 8
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- 238000010992 reflux Methods 0.000 claims description 8
- 238000010008 shearing Methods 0.000 claims description 8
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 8
- 239000008158 vegetable oil Substances 0.000 claims description 8
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 7
- 239000001639 calcium acetate Substances 0.000 claims description 7
- 229960005147 calcium acetate Drugs 0.000 claims description 7
- 235000011092 calcium acetate Nutrition 0.000 claims description 7
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000005543 nano-size silicon particle Substances 0.000 claims description 5
- 229920002635 polyurethane Polymers 0.000 claims description 5
- 239000004814 polyurethane Substances 0.000 claims description 5
- 239000004408 titanium dioxide Substances 0.000 claims description 5
- 239000008096 xylene Substances 0.000 claims description 5
- CYTYCFOTNPOANT-UHFFFAOYSA-N Perchloroethylene Chemical group ClC(Cl)=C(Cl)Cl CYTYCFOTNPOANT-UHFFFAOYSA-N 0.000 claims description 4
- 230000001804 emulsifying effect Effects 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 229950011008 tetrachloroethylene Drugs 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 235000010216 calcium carbonate Nutrition 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 235000010215 titanium dioxide Nutrition 0.000 claims description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 229920006335 epoxy glue Polymers 0.000 claims description 2
- 125000005375 organosiloxane group Chemical group 0.000 claims description 2
- 229920002545 silicone oil Polymers 0.000 claims description 2
- 238000007761 roller coating Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
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- 239000011159 matrix material Substances 0.000 abstract description 2
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- 230000000149 penetrating effect Effects 0.000 description 7
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- 238000010030 laminating Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
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- 150000001875 compounds Chemical class 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000012943 hotmelt Substances 0.000 description 2
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- 239000004005 microsphere Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
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- 239000007790 solid phase Substances 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920006231 aramid fiber Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229920006253 high performance fiber Polymers 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
Classifications
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/12—Stretch-spinning methods
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D1/00—Treatment of filament-forming or like material
- D01D1/02—Preparation of spinning solutions
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/02—Heat treatment
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
- D01D10/06—Washing or drying
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
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- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Artificial Filaments (AREA)
Abstract
The invention relates to a bulletproof material prepared from ultra-high molecular weight polyethylene and shear thickening fluid composite fibers, which is characterized in that firstly, the shear thickening fluid and spinning solvent or low-concentration ultra-high molecular weight polyethylene dissolution material are uniformly mixed, added into the ultra-high molecular weight polyethylene fiber spinning mixture according to a certain proportion, the composite gel fibers are obtained through extrusion molding, and then the ultra-high molecular weight polyethylene and shear thickening fluid composite fibers are obtained through extraction, drying or direct drying and multistage hot drawing; then, the ultra-high molecular weight polyethylene and the shear thickening fluid composite fiber are made into fabrics or sheets in the forms of warp knitting, weft knitting, weaving, non-weaving and the like; finally, the fabric or sheet is glued into soft bulletproof material by dipping or spraying or the like, or hot pressed into hard bulletproof material. According to the invention, the shear thickening fluid is introduced in the production process of the ultra-high molecular weight polyethylene fiber, so that the shear thickening fluid is uniformly dispersed in the ultra-high molecular weight polyethylene matrix and then is transferred to the surface of the fiber through high-power drafting, a nanoparticle layer is formed on the surface of the fiber, and the problems that the nanoparticle is settled and unevenly distributed after being placed for a long time are solved. The bulletproof material prepared by the ultra-high molecular weight polyethylene and the shear thickening fluid composite fiber has good bulletproof performance, and particularly has remarkable effect of reducing the dent.
Description
Technical Field
The invention relates to a bulletproof material prepared from ultra-high molecular weight polyethylene and shear thickening fluid composite fibers.
Background
The ultra-high molecular weight polyethylene fiber is a thermoplastic fiber with low glass transition temperature, has good toughness and absorbs energy in the plastic deformation process, so that the composite material of the ultra-high molecular weight polyethylene fiber has good mechanical property at high strain rate and low temperature, and has higher impact resistance than carbon fiber, aramid fiber and common glass fiber composite materials. The specific impact total absorption energy Et/p of the ultra-high molecular weight polyethylene fiber composite material is 1.8, 2.6 and 3 times that of carbon, aramid and E glass fibers respectively, and the bulletproof capacity of the ultra-high molecular weight polyethylene fiber composite material is 2.6 times that of an aramid armor structure. The impact strength of the ultra-high molecular weight polyethylene fiber is almost equal to that of nylon, and the energy absorption under high-speed impact is twice that of aramid (PPTA) fiber and nylon fiber. This property is very suitable for the production of ballistic resistant materials.
A shear thickening Fluid (SHEAR THICKENING Fluid, STF) is a non-newtonian Fluid. The viscosity of the fluid is closely related to the shear rate, and when the shear rate exceeds a certain critical value, its viscosity can increase drastically, i.e. so-called shear thickening occurs. The apparent viscosity of the shear thickening liquid can be greatly changed under high-speed impact, and even the apparent viscosity is changed from a liquid phase to a solid phase, so that the impact resistance of the solid is presented, and the shear thickening liquid can be quickly changed from the solid phase to the liquid phase after the impact force is eliminated, and the shear thickening effect is reversible. According to this characteristic, the shear thickening fluid can be applied in the field of impact resistance of materials, for example in the manufacture of ballistic resistant materials, protective equipment, vibration damping equipment and the like. The current research and experimental results show that the shear thickening fluid has a shear thinning phenomenon under the condition of low shear rate; whereas at high shear rates, shear thickening occurs. Barnes in the united kingdom summarizes the shear thickening of "dilatant fluid" (i.e. a shear thickening fluid) according to this experimental phenomenon. There are two microscopic mechanisms related to shear thickening, namely, one is the ODT mechanism (ordered to disordered) proposed by Hoffman, namely, shear thinning is caused by the increase of the order degree of particles in the system, and shear thickening is caused by the damage of the ordered structure of the particles in the system. Another mechanism is believed to be the shear thickening due to the formation of "particle clusters" in the system caused by the forces of the fluid, which increases the viscosity of the system.
Disclosure of Invention
At present, a liquid impact-resistant material prepared by compounding STF liquid and high-performance fiber fabrics is prepared by adopting a hot-melting material such as woven cloth, PVC and the like, laminating the hot-melting material on two sides of a three-dimensional sandwich material composite material by adopting a hot-melting rolling or hot-melting mould pressing process, laminating and sealing along edges to form a three-dimensional sandwich packaging bag, injecting the prepared STF liquid into a cavity of the three-dimensional sandwich structure, and laminating and sealing. STF liquid is filled into a three-dimensional sandwich composite material bag, nano microspheres in the STF liquid can be settled for a long time, so that the STF liquid is unevenly distributed, composition change is easy to occur, and the energy absorption characteristic of the material is seriously affected. And, the three-dimensional woven cloth material of the outer layer material is not easy to implement through heat sealing (hot melt rolling or hot melt molding), and has high cost and high energy consumption, and brings great difficulty to packaging.
The invention aims to solve the problems that nano microspheres are settled and unevenly distributed after being placed for a long time and the like by introducing a shear thickening fluid in the production process of the ultra-high molecular weight polyethylene fiber, so that the shear thickening fluid is uniformly dispersed in an ultra-high molecular weight polyethylene matrix and then is transferred to the surface of the fiber through high-power drafting, and a nano particle layer is formed on the surface of the fiber. The bulletproof material prepared by the ultra-high molecular weight polyethylene and the shear thickening fluid composite fiber has good bulletproof performance, and particularly has remarkable effect of reducing the dent.
The invention relates to a bulletproof material prepared from ultra-high molecular weight polyethylene and shear thickening fluid composite fibers, which is characterized in that firstly, the shear thickening fluid and spinning solvent or low-concentration ultra-high molecular weight polyethylene dissolution material are uniformly mixed, the mixture is added into the ultra-high molecular weight polyethylene fiber spinning mixture according to a certain proportion, the composite gel fibers are obtained through extrusion molding, and then the ultra-high molecular weight polyethylene and shear thickening fluid composite fibers are obtained through extraction, drying and multistage hot drawing or direct drying and multistage hot drawing.
The specific process is as follows:
a. firstly, adding one or more of 5-40 wt% of nano silicon dioxide, titanium dioxide, calcium carbonate and calcium acetate into a dispersion medium, emulsifying and dispersing by high-speed shearing, then heating, circulating reflux and filtering to remove large particles which cannot be uniformly dispersed, and finally evaporating or distilling to remove a low-boiling-point solvent to obtain a shear thickening fluid.
B. the low concentration ultra-high molecular weight polyethylene dissolving material is prepared by mixing the ultra-high molecular weight polyethylene with the concentration of 0.1-3 wt% with the spinning solvent and then slowly heating to 180-240 ℃.
C. And uniformly mixing the shear thickening fluid with a spinning solvent or a low-concentration ultrahigh molecular weight polyethylene solvent.
D. Adding the mixture obtained in the step c into the ultra-high molecular weight polyethylene spinning mixture according to the proportion of 5-25 wt%, and performing extrusion molding to obtain the composite gel fiber, wherein the solid content of the composite gel fiber is 3-25 wt%.
E. The ultra-high molecular weight polyethylene and shear thickening fluid composite fiber is obtained through extraction, drying and multistage hot drawing or direct drying and multistage hot drawing, wherein the inorganic nano particles account for 0.1 to 5 weight percent of the total weight of the ultra-high molecular weight polyethylene composite fiber.
Wherein the spinning solvent is one or more of vegetable oil, mineral oil, white oil, decalin, tetralin, dimethylbenzene and hydrocarbon solvent.
Wherein the low-concentration ultra-high molecular weight polyethylene dissolving material is prepared by mixing ultra-high molecular weight polyethylene with the concentration of 0.1-3 wt% with a spinning solvent and then slowly heating to 135-240 ℃.
Wherein the spinning extractant is one or more of tetrachloroethylene, dichloromethane, dimethylbenzene and hydrocarbon solvent.
Wherein the ultra-high molecular weight polyethylene and shear thickening fluid composite fiber is characterized in that the inorganic nano particles account for 0.1 to 5 weight percent of the total weight of the ultra-high molecular weight polyethylene composite fiber.
Wherein the particle size of the nano silicon dioxide, titanium dioxide, calcium carbonate and calcium acetate is 100-900 nanometers.
Wherein the dispersion medium is one or more of vegetable oil, mineral oil, white oil, silicone oil, decalin, tetrahydronaphthalene, xylene, hydrocarbon solvent, polyethylene glycol and glycerol.
Wherein the low boiling point solvent is one or more of water, ethanol and ammonia.
The specific implementation content is as follows:
Example 1
A. Firstly, adding 5wt% of calcium acetate with the particle diameter of 100 nanometers into a dispersion medium glycerol, emulsifying and dispersing through high-speed shearing, then heating, circulating reflux and filtering to remove large particles which cannot be uniformly dispersed in the dispersion medium glycerol, and finally evaporating or distilling to remove low-boiling-point solvent ethanol to obtain a shear thickening fluid.
B. the ultra-high molecular weight polyethylene with the concentration of 3 weight percent is mixed with the spinning solvent tetralin, and then the temperature is slowly increased to 135 ℃ to prepare the low-concentration ultra-high molecular weight polyethylene dissolving material.
C. mixing the shear thickening fluid with a spin solvent according to 1: and 4, uniformly mixing the materials in proportion.
D. Adding the mixture obtained in the step c into the ultra-high molecular weight polyethylene spinning mixture according to the proportion of 10wt%, and performing extrusion molding to obtain the composite gel fiber, wherein the solid content of the composite gel fiber is 25wt%.
E. the ultra-high molecular weight polyethylene and shear thickening fluid composite fiber is obtained through direct drying and multistage hot drawing, wherein the nano silicon dioxide accounts for 0.1 weight percent of the total weight of the ultra-high molecular weight polyethylene composite fiber.
F. The ultra-high molecular weight polyethylene and the shear thickening fluid composite fiber are warp-knitted to be made into a fabric.
G. The fabric is made into soft bulletproof material by dipping the fabric in shear thickening glue, and the glue content is 30wt%.
Example 2
A. Firstly, 20wt% of calcium carbonate with the particle diameter of 300 nanometers is added into decalin as a dispersion medium, dispersed by high-speed shearing and emulsification, then large particles which cannot be uniformly dispersed in the decalin are removed by heating, circulating reflux and filtering, and finally, low-boiling-point solvent ammonia is removed by evaporation or distillation to obtain a shear thickening fluid.
B. The ultra-high molecular weight polyethylene with the concentration of 1 weight percent is mixed with the spinning solvent and then slowly heated to 140 ℃ to prepare the low-concentration ultra-high molecular weight polyethylene dissolving material.
C. mixing the shear thickening fluid with a spin solvent according to 1: mixing uniformly in proportion of 1.
D. And c, adding the mixture obtained in the step c into the ultra-high molecular weight polyethylene spinning mixture according to the proportion of 5wt%, and performing extrusion molding to obtain the composite gel fiber, wherein the solid content of the composite gel fiber is 15wt%.
E. the ultra-high molecular weight polyethylene and shear thickening fluid composite fiber is obtained through direct drying and multistage hot drawing, wherein the inorganic nano particles account for 0.5 weight percent of the total weight of the ultra-high molecular weight polyethylene composite fiber.
F. The ultra-high molecular weight polyethylene and the shear thickening fluid composite fiber are subjected to weft knitting to form the fabric.
G. the fabric was coated with an epoxy glue in a spray-coating fashion, dried and hot-pressed to a hard ballistic material with a glue content of 2wt%.
Example 3
A. Firstly, adding 20wt% of 500-nanometer titanium dioxide with the diameter into a dispersion medium polyethylene glycol, dispersing by high-speed shearing and emulsifying, then heating, circularly refluxing, filtering to remove large particles which cannot be uniformly dispersed, and finally evaporating or distilling to remove low-boiling-point solvent water to obtain a shear thickening fluid.
B. The ultra-high molecular weight polyethylene with the concentration of 3 weight percent is mixed with spinning solvent mineral oil and then slowly heated to 240 ℃ to prepare the low-concentration ultra-high molecular weight polyethylene dissolving material.
C. mixing the shear thickening fluid with the spinning solution obtained in the step b according to the following ratio of 1: and 4, uniformly mixing the materials in proportion.
D. Adding the mixture obtained in the step c into the ultra-high molecular weight polyethylene spinning mixture according to the proportion of 25wt%, and performing extrusion molding to obtain the composite gel fiber, wherein the solid content of the composite gel fiber is 10wt%.
E. The ultra-high molecular weight polyethylene and shear thickening fluid composite fiber is obtained through xylene solvent extraction, drying and multistage hot drawing, wherein the inorganic nano particles account for 1 weight percent of the total weight of the ultra-high molecular weight polyethylene composite fiber.
F. The ultra-high molecular weight polyethylene and the shear thickening fluid composite fiber are woven into a fabric.
G. the fabric was coated with an acrylate gel in roll coating to make a hard ballistic material with a gel content of 15wt%.
Example 4
A. firstly, 15wt% of 300-diameter nano silicon dioxide and 5wt% of 300-diameter nano calcium acetate are added into dispersion medium white oil, the dispersion medium white oil is subjected to high-speed shearing, emulsification and dispersion, then large particles which cannot be uniformly dispersed in the dispersion medium white oil are removed through heating, circulating reflux and filtration, and finally, low-boiling-point solvent water is removed through evaporation or distillation, so that a shear thickening fluid is obtained.
B. mixing the shear thickening fluid with the solvent vegetable oil according to 2: mixing uniformly in proportion of 1.
C. And c, adding the mixture obtained in the step c into the ultra-high molecular weight polyethylene spinning mixture according to the proportion of 15wt%, and performing extrusion molding to obtain the composite gel fiber, wherein the solid content of the composite gel fiber is 10wt%.
D. The ultra-high molecular weight polyethylene and shear thickening fluid composite fiber is obtained through mixed extraction, drying and multistage hot drawing of methylene dichloride and hydrocarbon solvent, wherein the inorganic nano particles account for 2 weight percent of the total weight of the ultra-high molecular weight polyethylene composite fiber.
E. the ultra-high molecular weight polyethylene and the shear thickening fluid composite fiber are coated with polyurethane glue in an impregnation mode to be made into UD unidirectional sheets, and then the UD unidirectional sheets are subjected to orthogonal compounding to obtain the bulletproof sheets.
F. The ballistic resistant sheet obtained was then hot pressed to a hard ballistic resistant material with a gel content of 12wt%.
Example 5
A. Firstly, 40wt% of 300-nanometer calcium carbonate with the diameter is added into disperse medium vegetable oil, the disperse medium vegetable oil is subjected to high-speed shearing, emulsification and dispersion, then large particles which cannot be uniformly dispersed in the disperse medium vegetable oil are removed through heating, circulating reflux and filtration, and finally, low-boiling-point solvent water is removed through evaporation or distillation, so that the shear thickening fluid is obtained.
B. mixing the shear thickening fluid with spinning solvent white oil according to a ratio of 1: mixing uniformly in proportion of 1.
C. and c, adding the mixture obtained in the step c into the ultra-high molecular weight polyethylene spinning mixture according to the proportion of 15wt%, and performing extrusion molding to obtain the composite gel fiber, wherein the solid content of the composite gel fiber is 5wt%.
D. the ultra-high molecular weight polyethylene and shear thickening fluid composite fiber is obtained through mixing, extracting, drying and multistage hot drawing of tetrachloroethylene and hydrocarbon solvent, wherein the inorganic nano particles account for 3wt% of the total weight of the ultra-high molecular weight polyethylene composite fiber.
E. The ultra-high molecular weight polyethylene and the shear thickening fluid composite fiber are made into a sheet material through a non-woven form.
F. The sheet was hot pressed into a hard ballistic material with a gum content of 10wt% by impregnating the sheet with an organosiloxane resin gum.
Example 6
A. Firstly, 15wt% of 100-nanometer calcium acetate with the diameter and 25wt% of 100-nanometer silicon dioxide with the diameter are added into dispersion medium mineral oil, the dispersion medium mineral oil is subjected to high-speed shearing, emulsification and dispersion, then large particles which cannot be uniformly dispersed in the dispersion medium mineral oil are removed through heating, circulating reflux and filtration, and finally, low-boiling-point solvent water is removed through evaporation or distillation, so that the shear thickening fluid is obtained.
B. mixing the shear thickening fluid with a spin solvent according to 1: mixing uniformly in proportion of 1.
C. Adding the mixture obtained in the step c into the ultra-high molecular weight polyethylene spinning mixture according to the proportion of 25wt%, and performing extrusion molding to obtain the composite gel fiber, wherein the solid content of the composite gel fiber is 3wt%.
D. The ultra-high molecular weight polyethylene and shear thickening fluid composite fiber is obtained through tetrachloroethylene solvent extraction, drying and multistage hot drawing, wherein the inorganic nano particles account for 5 weight percent of the total weight of the ultra-high molecular weight polyethylene composite fiber.
E. The ultra-high molecular weight polyethylene and shear thickening fluid composite fiber is coated with polyurethane glue in an impregnation mode and mixed with the shear thickening glue in a ratio of 1:1 to form compound glue, and the compound glue is prepared into UD unidirectional sheets, and then the UD unidirectional sheets are subjected to orthogonal compounding to obtain the bulletproof sheets.
F. The resulting ballistic resistant sheet was then hot pressed to a hard ballistic resistant material with a gel content of 10wt%.
Comparative example 1
Adding ultra-high molecular weight polyethylene powder into decalin solvent according to the concentration of 7wt%, uniformly mixing, extruding and spinning by a double screw extruder to obtain gel fiber, and then directly drying and carrying out multistage hot drawing to obtain the ultra-high molecular weight polyethylene fiber. The ultra-high molecular weight polyethylene fiber is coated with polyurethane glue in an impregnation mode to be made into UD unidirectional sheets, and then the UD unidirectional sheets are subjected to orthogonal compounding to obtain the bulletproof sheets. The ballistic resistant sheet obtained was then hot pressed to a hard ballistic resistant material with a gel content of 12wt%.
Comparative example 2
Firstly, mixing the ultra-high molecular weight polyethylene with the concentration of 1wt% with a white oil spinning solvent, and then slowly heating to 180 ℃ to prepare the low-concentration ultra-high molecular weight polyethylene dissolving material. And adding the ultra-high molecular weight polyethylene powder into the low-concentration ultra-high molecular weight polyethylene dissolved material and the white oil solvent according to the concentration of 10wt%, uniformly mixing, extruding and spinning by a double-screw extruder to obtain gel fiber, and extracting by a hydrocarbon solvent, drying and carrying out multistage hot drawing to obtain the ultra-high molecular weight polyethylene fiber. The ultra-high molecular weight polyethylene fiber is coated with polyurethane glue in an impregnation mode to be made into UD unidirectional sheets, and then the UD unidirectional sheets are subjected to orthogonal compounding to obtain the bulletproof sheets. The ballistic resistant sheet obtained was then hot pressed to a hard ballistic resistant material with a gel content of 12wt%.
The ultra-high molecular weight polyethylene fibers prepared in the examples and the comparative examples were prepared into bulletproof test samples according to the standard requirements of GA141-2010 police body armor, and the test performances are shown in the following table.
Table 1 fibrous product ballistic performance comparison table
| Whether or not to penetrate | Depth of recess (mm) | |
| Example 1 | Not penetrating through | 15.7 |
| Example 2 | Not penetrating through | 11.8 |
| Example 3 | Not penetrating through | 13.2 |
| Example 4 | Not penetrating through | 17.5 |
| Example 5 | Not penetrating through | 9.6 |
| Example 6 | Not penetrating through | 10.4 |
| Comparative example 1 | Penetration through | / |
| Comparative example 2 | Not penetrating through | 27.5 |
The foregoing examples are provided for clarity of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While obvious variations or modifications are contemplated as falling within the scope of the present invention.
Claims (5)
1. The bulletproof material prepared from the ultra-high molecular weight polyethylene and the shear thickening fluid composite fiber is characterized in that firstly, the shear thickening fluid and a spinning solvent or a low-concentration ultra-high molecular weight polyethylene solvent are uniformly mixed, added into the ultra-high molecular weight polyethylene fiber spinning mixture according to a certain proportion, the composite gel fiber is obtained through extrusion molding, and then the ultra-high molecular weight polyethylene and the shear thickening fluid composite fiber is obtained through extraction, drying and multistage hot drawing or direct drying and multistage hot drawing; then, the ultra-high molecular weight polyethylene and the shear thickening fluid composite fiber are made into a fabric or sheet through warp knitting, weft knitting, weaving or non-weaving; finally, the fabric or sheet is made into soft bulletproof material by dipping, roller coating or spray coating glue, or hot pressed into hard bulletproof material;
The specific process is as follows:
a. Firstly, adding one or more of 5-40 wt% of nano silicon dioxide, titanium dioxide, calcium carbonate and calcium acetate into a dispersion medium, emulsifying and dispersing by high-speed shearing, then heating, circulating reflux and filtering to remove large particles which cannot be uniformly dispersed, and finally evaporating or distilling to remove a low-boiling-point solvent to obtain a shear thickening fluid;
b. The low-concentration ultra-high molecular weight polyethylene dissolving material is prepared by mixing the ultra-high molecular weight polyethylene with the concentration of 0.1-3 wt% with a spinning solvent and then slowly heating to 180-240 ℃; the spinning solvent is one or more of vegetable oil, mineral oil, white oil, decalin, tetrahydronaphthalene, xylene and hydrocarbon solvent;
c. Uniformly mixing the shear thickening fluid with a spinning solvent or a low-concentration ultra-high molecular weight polyethylene dissolved material;
d. Adding the mixture obtained in the step c into an ultra-high molecular weight polyethylene spinning mixture according to the proportion of 5-25 wt%, and performing extrusion molding to obtain composite gel fibers, wherein the solid content of the composite gel fibers is 3-25 wt%;
e. The ultra-high molecular weight polyethylene and shear thickening fluid composite fiber is obtained through extraction, drying and multistage hot drawing or direct drying and multistage hot drawing, wherein inorganic nano particles account for 0.1 to 5 weight percent of the total weight of the ultra-high molecular weight polyethylene composite fiber; the extractant is one or more of tetrachloroethylene, dichloromethane, xylene and hydrocarbon solvent;
f. Making the ultra-high molecular weight polyethylene and the shear thickening fluid composite fiber into a fabric or a sheet through warp knitting, weft knitting, weaving or non-weaving;
g. The fabric, sheet or composite fiber is made into soft bulletproof material by dipping or spraying glue or hot pressed into hard bulletproof material.
2. Ballistic resistant material according to claim 1, characterized in that the glue is added by dipping, roll coating or spraying in an amount of 2-30 wt% based on the weight of the ultra high molecular weight polyethylene fibres, the glue being one or more of a shear thickening glue, a polyurethane glue, an epoxy glue, an organosiloxane glue, an acrylate glue.
3. Ballistic resistant material according to claim 1, characterized in that the particle size of the nanosilica, titanium dioxide, calcium carbonate, calcium acetate is in the range of 100-900 nm.
4. The bulletproof material according to claim 1, wherein the dispersion medium is one or more of vegetable oil, mineral oil, white oil, silicone oil, decalin, tetralin, xylene, hydrocarbon solvent, polyethylene glycol, and glycerol.
5. Ballistic resistant material according to claim 1, wherein the low boiling point solvent is one or more of water, ethanol and ammonia.
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