CN116791229A - High-performance graphene modified aramid fiber and preparation method thereof - Google Patents
High-performance graphene modified aramid fiber and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 181
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 161
- 229920006231 aramid fiber Polymers 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000002131 composite material Substances 0.000 claims abstract description 68
- 239000006185 dispersion Substances 0.000 claims abstract description 59
- 239000000835 fiber Substances 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 36
- 239000011159 matrix material Substances 0.000 claims abstract description 24
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 12
- 239000002657 fibrous material Substances 0.000 claims abstract description 9
- 229920003235 aromatic polyamide Polymers 0.000 claims description 46
- 239000004760 aramid Substances 0.000 claims description 43
- 229920000642 polymer Polymers 0.000 claims description 43
- 239000007788 liquid Substances 0.000 claims description 32
- 238000009987 spinning Methods 0.000 claims description 30
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 18
- 229910052799 carbon Inorganic materials 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 238000011282 treatment Methods 0.000 claims description 14
- 238000005345 coagulation Methods 0.000 claims description 13
- 230000015271 coagulation Effects 0.000 claims description 13
- 239000011261 inert gas Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 229910052760 oxygen Inorganic materials 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000013329 compounding Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 239000010453 quartz Substances 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- MHABMANUFPZXEB-UHFFFAOYSA-N O-demethyl-aloesaponarin I Natural products O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=C(O)C(C(O)=O)=C2C MHABMANUFPZXEB-UHFFFAOYSA-N 0.000 claims description 5
- 238000002166 wet spinning Methods 0.000 claims description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 238000001237 Raman spectrum Methods 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 229930195733 hydrocarbon Natural products 0.000 claims description 3
- 150000002430 hydrocarbons Chemical class 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
- 229910052743 krypton Inorganic materials 0.000 claims description 3
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 2
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 2
- 239000000178 monomer Substances 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 238000005096 rolling process Methods 0.000 claims description 2
- 230000006641 stabilisation Effects 0.000 claims description 2
- 238000011105 stabilization Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims 1
- 150000002170 ethers Chemical class 0.000 claims 1
- 230000000977 initiatory effect Effects 0.000 claims 1
- 150000002989 phenols Chemical class 0.000 claims 1
- 210000002381 plasma Anatomy 0.000 description 13
- 230000008569 process Effects 0.000 description 9
- 230000001105 regulatory effect Effects 0.000 description 9
- 238000002156 mixing Methods 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000003014 reinforcing effect Effects 0.000 description 4
- 238000004804 winding Methods 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 239000011344 liquid material Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000010008 shearing Methods 0.000 description 3
- 238000001947 vapour-phase growth Methods 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000011538 cleaning material Substances 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 238000001241 arc-discharge method Methods 0.000 description 1
- 150000004984 aromatic diamines Chemical class 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000009940 knitting Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 description 1
- 229910021392 nanocarbon Inorganic materials 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000012763 reinforcing filler Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
-
- 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
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/90—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides
- D01F6/905—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyamides of aromatic polyamides
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Textile Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Fibers (AREA)
Abstract
The invention discloses an aramid fiber/graphene composite fiber material, which comprises, by mass, 95-99.9% of aramid fiber and 0.1-5% of graphene, wherein the size of the graphene is 50-300 nm, and the number of layers is 1-5, and the graphene is continuously prepared by a microwave plasma chemical vapor deposition method. Also discloses a specific preparation method of the composite fiber material. The invention can effectively realize good dispersion of graphene in the aramid fiber matrix, and the tensile strength and the elongation at break of the composite fiber are greatly improved.
Description
Technical Field
The invention belongs to the technical field of fiber preparation, and particularly relates to a graphene/aramid composite fiber and a preparation method thereof.
Background
An aromatic polyamide fiber, abbreviated as Aramid fiber (English name), is a long-chain polymer generated by the reaction of aromatic diamine and aromatic diacid chloride, wherein the molecular main chain at least contains 85% of amide groups and a long-chain structure with two aromatic rings connected. Among them, for example, meta-aramid has outstanding high temperature resistance, flame retardance and insulativity, and is mainly applied to the fields of high temperature protective clothing, electric insulation, high temperature filtration and the like. The fiber has the characteristics of good flexibility, easiness in knitting and the like, but has a certain gap between mechanical properties compared with those of similar para-aramid fiber and heterocyclic aramid fiber, and limits the application of the fiber in the fields of high-temperature protection and the like. In order to further improve the mechanical properties of the multi-grade aramid fiber, the multi-grade aramid fiber needs to be modified, and finally the purpose of optimizing the comprehensive properties of meta-aramid fiber is achieved.
Graphene is of sp 2 Two-dimensional nano carbon material with hybridized structure and extremely high specific surface area (-2630 m) 2 ·g -1 ) Low density (-0.77 g cm) -1 ) Excellent mechanical properties (breaking strength 130GPa, young's modulus 1.0 TPa) and thermal conductivity (5300 W.m) -1 ·K -1 ). Several patents have reported on graphene modified para-aramid fiber, such as patent 201410269027.0, "a method for grafting and modifying aramid fiber on graphene oxide surface", and patent 201711022075.X, "a graphene reinforced para-aramid fiber bundle and preparation method thereof", all adopt graphene to compound aramid fiber, and indexes such as strength, elongation at break, antibacterial property and far infrared emissivity of the compounded aramid fiber are improved.
Currently the main supported form of graphene is surface coated. The main reason is that the polymerization and spinning process of the aramid fiber involves an organic solvent system, but the graphene is insoluble in water and organic solvent, and because the surface atoms have higher surface energy and surface binding energy, the dispersion is poor, large agglomerates are easy to form, the aramid fiber is only 10-20 mu m in filament, the effective dispersion of the graphene is difficult to realize by the micron-sized graphene and the common blending method, and the subsequent spinnability and the comprehensive mechanical properties of the fiber are seriously affected by the poor dispersion. Based on the above considerations, how to obtain high-performance aramid/graphene composite fibers with dispersibility number is a problem to be solved.
Disclosure of Invention
The invention aims to provide a graphene/aramid composite fiber and a method thereof. The method can overcome the dispersion problem of graphene in the aramid fiber matrix, and the composite aramid fiber with uniform graphene dispersion, high strength and high toughness is prepared.
The invention provides an aramid fiber/graphene composite fiber material, which comprises, by mass, 95-99.9% of aramid fiber and 0.1-5% of graphene, wherein the size of the graphene is 50-300 nm, and the number of layers is 1-5.
According to an embodiment of the invention, the carbon content of the graphene is greater than 99.5wt% and the oxygen content is less than 0.5wt%;
preferably, the specific surface area of the graphene is greater than 200m 2 ·g -1 ；
Preferably, in the raman spectrum of the graphene, the D peak (1340 cm -1 Nearby) intensity and G peak (1580 cm -1 Near) intensity ratio less than 0.5,2D peak (2700 cm -1 Near) the ratio of intensity to G peak intensity is greater than 0.6.
According to an embodiment of the invention, the graphene is continuously prepared by a microwave plasma chemical vapor deposition method, and the specific preparation method is as follows:
1) Introducing inert gas into the microwave plasma chemical vapor deposition system to generate plasma;
2) Introducing a carbon source into a microwave plasma chemical vapor deposition system to perform vapor phase growth of graphene;
wherein the inert gas is selected from one or more of argon, krypton and xenon;
the carbon source is selected from one or more of hydrocarbon, alcohol, ether, ketone and phenol;
the flow rate of the inert gas is 1200-2000 sccm, and the flow rate of the carbon source gas is 2-100 sccm;
the microwave power variation range of the microwave plasma chemical vapor deposition system is 200-2000W.
The invention also provides a preparation method of the composite fiber material, which comprises the following preparation steps:
s1, pre-dispersing graphene in a solvent system;
s2, compounding graphene and an aramid fiber matrix to obtain a composite polymer solution;
s3, carrying out secondary treatment and secondary dispersion on the composite polymer solution obtained in the step S2;
and S4, spinning the composite polymer solution obtained in the step S3.
According to an embodiment of the present invention, in the step S1, a solvent DMAC (N, N-dimethylacetamide) for polymerizing aramid fiber is selected to disperse graphene, and the graphene is dispersed under the protection of inert gas by using a high-power ultrasonic device, where the dispersion concentration is as follows: 0.1 to 5 weight percent, the ultrasonic power is as follows: 300-600W, the ultrasonic time is: and 1-5 h. The inert gas may be one or more of nitrogen, argon, helium, carbon dioxide.
According to an embodiment of the present invention, in the step S2, the polymerization solution is added into the three-neck flask, dry nitrogen is introduced into the three-neck flask, and stirring is performed by using a polytetrafluoroethylene stirring paddle, the graphene dispersion is gradually added in a plurality of steps, and the graphene accounts for the aramid fiber matrix: 0.1 to 5 percent. The stirring time is 1-3 h, and the composite polymer liquid with uniform color can be obtained.
According to an embodiment of the invention, the aramid polymerization liquid is meta-aramid polymerization liquid; the meta-aramid polymerization solution takes m-phthaloyl chloride and m-phenylenediamine monomers as raw materials and DMAC as a solvent; the viscosity of the aramid spinning solution is 3-12 ten thousand centipoise.
The compound polymerization solution obtained in the step S2 is a uniform mixed system of graphene and aramid fiber, but the graphene is compounded in the high-viscosity aramid fiber system at the moment and is redispersed, so that the shearing force of the mechanical mixing mode cannot ensure uniform monodispersion of the graphene in the aramid fiber system. In a large number of experiments attempted in the earlier stage, if the dispersion liquid is directly spun, the problems of broken filaments, hole blockage of a spinneret plate, more broken filaments, low mechanical properties of the bundle filaments and the like can occur. Accordingly, in the present invention, it is proposed to perform the secondary treatment and the secondary dispersion on the composite polymer liquid obtained through step S2 through step S3. According to an embodiment of the present invention, in the step S3, the composite polymer solution obtained in the step S2 is first subjected to standing stabilization for 12 to 24 hours; the main purpose of the step is to ensure the stable state of the graphene in the aramid matrix, especially in the meta-aramid matrix, and the rest can effectively remove redundant bubbles and the like generated in the stirring process of the step S2. And then carrying out secondary dispersion treatment on the composite polymer liquid by using high-viscosity dispersion equipment, wherein the high-viscosity dispersion equipment is one of a three-roller machine and a high-dispersion threaded sleeve double-screw extruder, the treatment times are 3-8 times, the fineness is less than 5 mu m after secondary dispersion, and the graphene has the advantages of excellent dispersibility, no bubbles, good spinnability and the like, and can be directly applied to wet spinning production.
Preferably, the high-viscosity dispersing equipment is a three-roller machine, the slit distance of the three-roller machine is 5-10 mu m, and the treatment times are 3-8 times;
preferably, the high-viscosity dispersing device is a high-viscosity dispersing threaded sleeve double-screw extruder, the extruding temperature of the double-screw extruder is 25-40 ℃, the rotating speed of the screw is 30-80 rpm, and the cycle time is 10-60 min.
According to an embodiment of the present invention, the spinning method in the step S4 is wet spinning.
According to an embodiment of the present invention, in the step S4, the composite polymer solution obtained through the treatment of the step S3 is poured into a spinning cylinder, extruded under a certain pressure, the extruded filament bundles are subjected to phase separation in a coagulation bath and form a skin-core structure, and stretched, washed and collected in a hot water bath by a certain multiple; and washing the collected silk, drying, performing hot stretching treatment, and finally rolling.
According to the invention, the thin-layer powder graphene with the magnitude of tens to hundreds of nanometers is selected as the reinforcing phase, so that the fiber size (10-20 mu m) of the aramid fiber can be effectively matched, the defects are fewer, the oxygen content is low, and good dispersion in an aramid matrix can be effectively realized. The tensile strength and the elongation at break of the aramid fiber/graphene composite fiber are greatly improved, and the graphene can form firm interface combination with an aramid fiber matrix after pre-dispersion and secondary dispersion. And the strength of the aramid fiber can be improved by about 40-58% with a small addition amount, and the elongation at break is improved by about 70-90%. The preparation method of the graphene/aramid composite fiber provided by the invention is characterized in that the graphene is pre-dispersed and the composite slurry is secondarily dispersed, when the graphene and the aramid are compounded, the graphene powder is simply dispersed in a solvent used by an aramid spinning solution, and then the graphene powder and the aramid spinning solution are directly compounded and secondarily dispersed, so that the solvent is not required to be removed, and the preparation method has the characteristics of simplicity in operation and easiness in large-scale production, and can successfully and controllably disperse the graphene which has large specific surface area and is difficult to disperse in an aramid polymer resin system with higher viscosity, thereby providing a foundation for developing the light, high-strength and functional graphene/meta-aramid composite fiber.
Drawings
The accompanying drawings are included to provide a further illustration and explanation of the invention, and together with the detailed description of the invention given below, are not to be taken in a limiting sense.
FIG. 1 is a Raman spectrum of graphene of preparation example 1;
FIG. 2 is a scanning electron microscope image of graphene of preparation example 1;
FIG. 3 is a transmission electron microscope image of the graphene/meta-aramid composite fiber of example 1;
FIG. 4 is a mercerized photograph of the graphene/meta-aramid composite fiber of example 1;
FIG. 5 is a graph representing the tensile properties of the graphene/meta-aramid composite fiber of example 1, which is a mercerized photograph of the graphene/meta-aramid composite fiber of example 1;
fig. 6 is a graph showing the tensile properties of the graphene/meta-aramid composite fibers of examples 1 and 2 and comparative examples 1 and 2.
The specific embodiment is as follows:
the invention is further illustrated by, but is not limited to, the following specific examples which are provided to aid in the understanding of the invention and are not intended to limit the scope of the invention.
The invention provides a preparation method of an aramid fiber/graphene composite fiber, wherein the weight percentage of the aramid fiber in the composite fiber is 95-99.9%, and the weight percentage of the graphene is 0.1-5%. Wherein the grapheme carbon content is more than 99.5 weight percent and the oxygen content is less than 0.5 weight percent. The particle size of the graphene powder is 50-300 nm, the number of layers is 1-5, and the specific surface area of the graphene is more than 200m 2 ·g -1 . The graphene is used as the reinforcing filler to effectively reinforce the matrix material, and the higher the intrinsic mechanical property of the graphene is, the better the reinforcing effect on the matrix is. However, the existing graphene reinforced base materials based on the blending mode are basically prepared from graphene oxide or reduced graphene oxide with higher oxygen content to ensure dispersibility, but according to theoretical calculation, the mechanical strength of the graphene with high carbon content (more than 95 wt%) is about 3 times that of the reduced graphene oxide. Therefore, the invention selects the thin powder graphene with the magnitude of tens to hundreds of nanometers as the reinforcing phase, can effectively match the filament forming size (10 to 20 mu m) of the aramid fiber, has fewer defects and low oxygen content, and can effectively realize good dispersion in the aramid matrix.
The high carbon-oxygen ratio graphene can be prepared by a microwave plasma chemical vapor deposition method. Specifically, inert gas is introduced into a microwave plasma chemical vapor deposition system to generate plasma; introducing a carbon source into a microwave plasma chemical vapor deposition system to perform vapor phase growth of graphene; the inert gas used for generating the plasmas is selected from one or more of argon, krypton and xenon, the carbon source is selected from one or more of hydrocarbon, alcohol, ether, ketone and phenol, the flow rate of the inert gas is 1200-2000 sccm, the flow rate of the carbon source gas is 2-100 sccm (sccm, standard milliliters per minute), the variation range of the microwave power of the microwave plasma chemical vapor deposition system is 200-2000W in the vapor phase growth process of the graphene, and the quality and morphology of the graphene and the conversion rate of the carbon source can be influenced by the power of the microwaves. In addition, the preparation method of the graphene used in the invention is environment-friendly, and the problems of environmental pollution and the like generated in the reduction process when the graphene is reinforced by using reduced graphene oxide and the like are avoided.
Of course, the present invention can ensure the required graphene parameter characteristics, and can effectively reinforce the fiber matrix material, namely the high-quality graphene prepared by arc discharge method and radio frequency method, which belongs to the present invention concept.
When the graphene and the aramid fiber are compounded, the graphene powder is simply dispersed in the solvent used by the aramid fiber spinning solution, and then the graphene powder and the aramid fiber spinning solution are directly compounded and secondarily dispersed, so that the solvent is not required to be removed, and the method is simple and easy to implement. The addition of the graphene can increase the viscosity of the system, the problem of viscosity reduction caused by the introduction of graphene dispersion liquid can not occur, the graphene does not need reduction and other treatments, the process is simple, and the control and the system amplification are easy to link. The secondary dispersion mainly comprises a secondary shearing dispersion process performed by a three-roll machine, a double-screw extruder or the like. Through compounding, the graphene is easy to form flocculation phenomenon caused by viscosity difference in the aramid fiber matrix, and nano-scale dispersion of graphene sheets in the aramid fiber matrix can be realized through shearing and dispersing of high-viscosity materials. Of course, the secondary dispersion method still depends on the selection of the size of graphene, for example, micron-sized graphene oxide and the like are dispersed in a high-viscosity matrix by a three-roller machine, and extrusion is easy to occur at a slit to cause microscopic lamination due to larger size, so that the subsequent spinning process is not facilitated. Wherein, preferably, the slit distance of the three-roller machine is 5-10 mu m, and the treatment times are 3-8 times; the extrusion temperature of the double-screw extruder is 25-40 ℃, the screw rotating speed is 30-80 rpm, and the circulation time is 10-60 min.
The aramid fiber/graphene composite fiber is prepared by adopting wet spinning, and has requirements on the extrusion speed of a spinning main machine, the coagulation bath temperature, the water bath temperature, the coagulation bath stretching multiplying power, the water bath stretching multiplying power, the heat treatment temperature and the heat treatment stretching multiplying power. The inventor of the present patent has determined suitable process conditions by elucidation and found that optimum spinning conditions are obtained. Wherein, the preferable extrusion speed of the spinning main machine is 2-6 m/min, the temperature of the coagulating bath is 20-50 ℃, the temperature of the hot water bath is 60-100 ℃, the stretching multiplying power of the coagulating bath is 0.2-0.8, the stretching multiplying power of the hot water bath is 1-3, the temperature of the heat treatment is 270-320 ℃, and the stretching multiplying power of the heat treatment is 1-4.
The tensile strength and the elongation at break of the aramid fiber/graphene composite fiber are greatly improved, and the graphene can form firm interface combination with an aramid fiber matrix after pre-dispersion and secondary dispersion. And the strength of the aramid fiber can be improved by about 40-58% with a small addition amount, and the elongation at break is improved by about 70-90%.
In summary, the invention provides the aramid fiber/graphene composite fiber and the preparation method thereof, and the composite fiber material with improved mechanical properties is prepared by adopting graphene with specific size and quality and through the processes of secondary dispersion and wet spinning, and has great prospect in the industrial production process of graphene-based composite materials.
The invention will be further illustrated by the following specific examples, which are not intended to be limiting in any way. Unless otherwise specified, the experimental methods used in the following examples or preparations are all conventional methods. Materials, reagents and the like used in the following examples or preparations are all commercially available.
Preparation example 1
The preparation example is used for explaining the preparation process of the high-quality graphene powder.
The invention utilizes a microwave plasma chemical vapor deposition system, and introduces 1500sccm argon to remove the residual air in the system. Argon plasma is generated by adjusting the microwave power to 800W and triggering the system, and then 4sccm methane is introduced into the system. At the moment, the system generates corona discharge phenomenon, meanwhile, the graphene powder continuously floats away from the system at the tail end of the quartz tube, and the graphene powder is collected. After about 30 minutes of reaction, the methane flowmeter is closed, and more graphene powder is left on the quartz tube wall in the microwave reaction cavity area. At the same power, the system is connectedAfter 8sccm of oxygen is added, no obvious black substance residue is found on the wall of the quartz tube in the reaction cavity region after about 1-2 min, which indicates that the graphene residue in the region is completely etched. And continuously repeating the steps for about 5 hours to obtain a large amount of powder graphene. The obtained graphene has the carbon content of 98.85%, the oxygen content of 1.15%, the number of sheets of 3-5 layers and the specific surface area of 240m 2 /g)。
FIG. 1 is a Raman spectrum of graphene of preparation example 1, which is seen to be of extremely high quality, wherein I D /I G <0.4，I 2D /I G >0.65。
Fig. 2 is a Scanning Electron Microscope (SEM) image of graphene of preparation example 1, and it can be seen that the size of graphene thereof is between 50 and 300 nm.
Example 1
This example is used to illustrate the preparation of aramid/graphene composite fiber material using the graphene of preparation example 1.
The graphene prepared in preparation example 1 is selected to be dispersed in DMAc solution, and the dispersion liquid with the concentration of 0.1 weight percent is prepared under the protection of nitrogen by using ultrasonic dispersing equipment with the ultrasonic power of 300W. Selecting a three-neck flask, weighing a proper amount of meta-aramid polymer liquid, wherein the viscosity of the meta-aramid polymer liquid is 12 ten thousand centipoise, then adding the graphene dispersion liquid into the polymer liquid for 5 times under the stirring of a polytetrafluoroethylene stirring paddle, stirring for 1h to obtain graphene/meta-aramid composite polymer liquid with uniform color and smooth surface, and then standing the composite polymer liquid for 12h.
Under the protection of nitrogen, the composite polymer liquid material after standing is put into a three-roller machine for secondary dispersion, the width of a slit between rollers is adjusted by a hand wheel, the slit is adjusted from full closing to full opening, and the operation process is careful to observe whether leakage occurs. And the width between the rollers is regulated, the width between the front roller and the middle roller is regulated to be 10 mu m, the width between the middle roller and the rear roller is regulated to be 5 mu m, the material is taken after grinding is finished, the fineness is tested, the operation is stopped when the fineness is below 5 mu m, the polymer liquid is collected, and the viscosity after compounding is 8 ten thousand centipoise.
And (3) putting the composite polymer solution after secondary dispersion into a spinning host, regulating the temperature of circulating water of the host to 40 ℃, and carrying out conventional spinning, primary coagulation bath, secondary coagulation bath, water washing and drying after the polymer solution is leveled. And thermally stretching the as-spun filaments at 300℃for 30s. And then winding into a filament, wherein the filament is a graphene/meta-aramid composite fiber with the mass fraction of graphene of 1%, the breaking strength of the filament is 4.4cN/dtex, and the breaking elongation of the filament is 22%. The obtained composite fiber is ultrathin sliced, and the interface of the composite fiber is observed by a Transmission Electron Microscope (TEM), so that the graphene nano-sheets are uniformly dispersed and matched with the aramid fiber matrix (shown in figure 3) and the powder size (50-300 nm), and the uniform distribution of the graphene in the composite fiber prepared by the method is shown, and the agglomeration phenomenon is avoided.
Example 2
Graphene is selected to be dispersed in DMAC solution, ultrasonic dispersion equipment is utilized, ultrasonic power is 400W, and dispersion liquid with concentration of 5wt% is prepared under the protection of nitrogen. And selecting a three-neck flask, weighing a proper amount of meta-aramid polymer liquid, wherein the viscosity of the meta-aramid polymer liquid is 12 ten thousand centipoise, then adding the graphene dispersion liquid into the polymer liquid for 5 times under the stirring of a polytetrafluoroethylene stirring paddle, and stirring for 1.5 hours to obtain the graphene/meta-aramid composite polymer liquid with uniform color and smooth surface.
Under the protection of nitrogen, the polymer liquid material is put into a high-dispersion threaded sleeve double-screw extruder for secondary dispersion, equipment is preheated in advance, the temperature is kept at 40 ℃ and above 40 minutes, the initial material is a cleaning material, the feeding speed and the screw rotating speed are regulated to 80rpm after the discharging speed is stable, the material mixing is finished after 20 minutes, the material taking test fineness is finished, the operation is stopped when the fineness is below 5 mu m, the polymer liquid is collected, and the viscosity is 8 ten thousand centipoise after the compounding.
And (3) putting the composite polymer solution after secondary dispersion into a spinning host, regulating the temperature of circulating water of the host to 40 ℃, and carrying out conventional spinning, primary coagulation bath, secondary coagulation bath, water washing and drying after the polymer solution is leveled. And thermally stretching the as-spun filaments at 300℃for 30s. And then winding into a filament, wherein the filament is a meta-aramid/graphene composite fiber with the graphene mass fraction of 1.5%, the breaking strength of the filament is 4.0cN/dtex, and the breaking elongation of the filament is 18%. As shown in fig. 4, the color of the composite fiber is uniform, and phenomena such as hole blocking and fineness reduction do not occur in the spinning process, which indicates that the composite spinning solution has excellent spinnability. The mechanical properties of the fiber are obviously improved compared with those of the pure meta-aramid fiber, as shown in figure 5.
Comparative example 1
Graphene oxide (size 2-10 μm, carbon content of graphene 60% and oxygen content of 40%) obtained from Li Tena m graphene company was selected, and the graphene oxide/meta-aramid composite polymer liquid was obtained according to the dispersion method in example 1.
Under the protection of nitrogen, the polymer liquid material is put into a high-dispersion threaded sleeve double-screw extruder for secondary dispersion, equipment is preheated in advance, the temperature is kept at 40 ℃ and above 40 minutes, the initial material is a cleaning material, the feeding speed and the screw rotating speed are regulated to 80rpm after the discharging speed is stable, the material mixing is finished after 20 minutes, the material taking test fineness is finished, the operation is stopped when the fineness is below 5 mu m, the polymer liquid is collected, and the viscosity is 10 ten thousand centipoise after the compounding.
And (3) putting the composite polymer solution after secondary dispersion into a spinning host, regulating the temperature of circulating water of the host to 40 ℃, and carrying out conventional spinning, primary coagulation bath, secondary coagulation bath, water washing and drying after the polymer solution is leveled. And thermally stretching the as-spun filaments at 300℃for 30s. And then winding into a filament, wherein the filament is a reduced graphene oxide/meta-aramid fiber composite fiber with the mass fraction of graphene of 1%, the breaking strength of the filament is 2.4cN/dtex, and the breaking elongation of the filament is 8.5%.
Comparative example 2
The compounded graphene/meta-aramid composite polymer solution obtained by the dispersion method in example 1 was not subjected to secondary dispersion, and the viscosity of the spinning solution after compounding was 7 ten thousand centipoise.
And (3) putting the composite polymer solution which is not subjected to secondary dispersion into a spinning host, regulating the temperature of circulating water of the host to 40 ℃, and carrying out conventional spinning, primary coagulation bath, secondary coagulation bath, water washing and drying after the polymer solution is leveled. And thermally stretching the as-spun filaments at 400℃for 30s. And then winding into a filament, wherein the filament is a reduced graphene oxide/meta-aramid fiber composite fiber with the mass fraction of graphene of 1%, the breaking strength of the filament is 1.8cN/dtex, and the breaking elongation of the filament is 5.7%.
Fig. 6 is a graph showing the mechanical properties of meta-aramid/graphene composite fibers of examples 1 and 2 and comparative examples 1 and 2, specifically including both tensile strength and elongation at break. As can be seen from the graph, compared with the graphene powder sold in the market, the graphene prepared by the method has an obvious effect of enhancing the mechanical properties of the aramid fiber matrix. When larger-size graphene oxide is used as a reinforcing phase, the tensile strength of meta-aramid fiber is slightly reduced, and particularly the elongation at break is obviously reduced, mainly because the large-size graphene has poor dispersibility in a matrix, and the size of the large-size graphene is similar to the diameter of the aramid fiber, so that stress concentration is easily caused in the stretching process, and the large-size graphene becomes a failure site. The aramid fiber/graphene composite spinning solution which is not subjected to secondary dispersion is small in viscosity and poor in uniformity, holes are easily blocked in the spinning process to cause yarn breakage, and the tensile strength and the elongation at break of the spun fiber are obviously reduced, mainly because the graphene which is not subjected to secondary dispersion is seriously agglomerated, and an effective interface is not formed between the surface of the graphene and an aramid fiber matrix, so that the performance is reduced.
In conclusion, the graphene used in the invention has the advantages of low defect degree, high carbon content and the like, and the size is tens to hundreds of nanometers, and the dispersion method can realize efficient dispersion in the aramid fiber matrix. Compared with other preparation methods such as a method of coating graphene on the surface of aramid fiber, the blended yarn fiber has the advantages of strong binding force, uniform texture, uneasy falling of graphene and the like. And the graphene has higher quality, and compared with graphene oxide and reduced graphene oxide with higher oxygen content, the graphene oxide and reduced graphene oxide can mechanically strengthen fibers. The method has the advantages that the process is simple, the solvent does not need to be removed after the graphene dispersion liquid is compounded with the matrix, the used secondary dispersion equipment is simple, the system amplification is facilitated, and the method has quick production capacity. The composite fiber prepared by the invention can realize the great improvement of the breaking strength and the breaking elongation under the condition of small graphene addition amount of 1 percent and the like, and has good industrialized prospect.
Claims (10)
1. The aramid/graphene composite fiber material is characterized in that the composite fiber comprises, by mass, 95-99.9% of aramid and 0.1-5% of graphene, wherein the size of the graphene is 50-300 nm, and the number of layers is 1-5.
2. The composite fiber material of claim 1, wherein the grapheme carbon content is greater than 99.5wt% and the oxygen content is less than 0.5wt%;
preferably, the specific surface area of the graphene is greater than 200m 2 ·g -1 ；
Preferably, in the raman spectrum of the graphene, the D peak (1340 cm -1 Nearby) intensity and G peak (1580 cm -1 Near) intensity ratio less than 0.5,2D peak (2700 cm -1 Near) the ratio of intensity to G peak intensity is greater than 0.6.
3. The composite fiber material according to claim 1 or 2, wherein the graphene is continuously prepared by a microwave plasma chemical vapor deposition method, and the specific preparation method is as follows:
firstly, introducing inert gas to remove residual air in a system, generating plasma by adjusting a microwave power initiation system, then introducing a carbon source into the system, generating a corona discharge phenomenon by the system, continuously drifting graphene powder away from the system at the tail end of a quartz tube, and collecting the graphene powder; after a certain time of reaction, closing a carbon source flowmeter, and observing that more graphene powder remains on the quartz tube wall of the microwave reaction cavity area; under the same power, oxygen is introduced into the system, no obvious black substance residue is visible on the quartz tube wall of the reaction cavity region after about 1-2 min, the fact that the graphene residue in the region is completely etched is shown, and the steps are continuously repeated for reacting for about 5h, so that a large amount of powder graphene is obtained;
wherein the inert gas is selected from one or more of argon, krypton and xenon, preferably argon;
the carbon source is selected from one or more of hydrocarbons, alcohols, ethers, ketones and phenols, preferably methane;
the inert gas flow is 1200-2000 sccm, preferably 1500sccm; the flow rate of the carbon source gas is 2-100 sccm, preferably 4sccm;
the microwave power of the microwave plasma chemical vapor deposition system ranges from 200W to 2000W, preferably 800W.
4. A method of producing a composite fibre material according to any one of claims 1 to 3, comprising the steps of:
s1, pre-dispersing graphene in a solvent system;
s2, compounding graphene and an aramid fiber matrix to obtain a composite polymer solution;
s3, carrying out secondary treatment and secondary dispersion on the composite polymer solution obtained in the step S2;
and S4, spinning the composite polymer solution obtained in the step S3.
5. The method according to claim 4, wherein in the step S1, the graphene is dispersed by DMAC (N, N-dimethylacetamide) under the protection of inert gas by using a high-power ultrasonic apparatus, and the dispersion concentration is as follows: 0.1 to 5 weight percent;
the ultrasonic power is as follows: 300-600W; the ultrasonic time is as follows: 1 to 5 hours;
the inert gas is one or more of nitrogen, argon, helium and carbon dioxide.
6. The preparation method according to claim 4, wherein in the step S2, the aramid polymer liquid is added into a three-necked flask, dry nitrogen is introduced into the three-necked flask, and stirring is performed by using a polytetrafluoroethylene stirring paddle, and the graphene dispersion liquid is gradually added in a plurality of times, wherein the stirring time is 1-3 hours, so that the composite polymer liquid with uniform color is obtained;
the graphene accounts for 0.1-5% of the aramid fiber matrix.
7. The method of claim 6, wherein the aramid polymerization liquid is a meta-aramid polymerization liquid; the meta-aramid polymerization solution takes m-phthaloyl chloride and m-phenylenediamine monomers as raw materials and DMAC as a solvent; the viscosity of the aramid polymer liquid is 3-12 ten thousand centipoise.
8. The method according to claim 4, wherein in the step S3, the composite polymer solution obtained in the step S2 is first allowed to stand for 12 to 24 hours for stabilization; then, carrying out secondary dispersion treatment on the composite polymer liquid by using high-viscosity dispersion equipment, wherein the high-viscosity dispersion equipment is one of a three-roll machine and a high-dispersion threaded sleeve double-screw extruder, and the fineness requirement is less than 5 mu m after secondary dispersion;
preferably, the viscosity dispersing device is a three-roller machine, the slit distance of the three-roller machine is 5-10 mu m, and the treatment passes are 3-8 times;
preferably, the viscosity dispersing device is a high-dispersion threaded sleeve double-screw extruder, the extrusion temperature of the double-screw extruder is 25-40 ℃, the screw rotating speed is 30-80 rpm, and the circulation time is 10-60 min.
9. The method according to claim 4, wherein the spinning method in step S4 is wet spinning.
10. The method according to claim 9, wherein in the step S4, the composite polymer solution obtained by the treatment of the step S3 is poured into a spinning cylinder, extruded under a certain pressure, the extruded filament bundles are phase-separated in a coagulation bath and form a skin-core structure, and stretched in a hot water bath, washed with water and collected; washing and drying the collected silk, performing hot stretching treatment, and finally rolling;
preferably, the extrusion speed of the spinning main machine is 2-6 m/min, the coagulation bath temperature is 20-50 ℃, the hot water bath temperature is 60-100 ℃, the hot water bath stretching multiplying power is 1-3, the heat treatment temperature is 270-320 ℃, and the heat treatment stretching multiplying power is 1-4.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117385488A (en) * | 2023-12-12 | 2024-01-12 | 电子科技大学 | Flame-retardant and strength-enhanced graphene modified aramid fiber and preparation method thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013011250A1 (en) * | 2011-07-21 | 2013-01-24 | Arkema France | Graphene-based conductive composite fibres |
| KR20150066180A (en) * | 2013-12-06 | 2015-06-16 | 코오롱인더스트리 주식회사 | Method of manufacturing aramid fiber with excellent tenacity and aramid fiber manufactured thereby |
| CN106498538A (en) * | 2016-11-18 | 2017-03-15 | 株洲时代新材料科技股份有限公司 | The preparation method and applications of high-termal conductivity aromatic polyamide fibre |
| CN106835332A (en) * | 2016-09-14 | 2017-06-13 | 济南圣泉集团股份有限公司 | Compound para-aramid fiber of high performance Graphene and preparation method thereof, application |
| WO2018166477A1 (en) * | 2017-03-15 | 2018-09-20 | 山东圣泉新材料股份有限公司 | Modified fibre product, preparation method therefor and use thereof |
| CN109056098A (en) * | 2018-08-07 | 2018-12-21 | 李解 | A kind of preparation method of high performance graphene aramid fiber and thus obtained high performance graphene aramid fiber |
| CN110451496A (en) * | 2019-09-17 | 2019-11-15 | 北京石墨烯研究院 | A method of continuously high-volume preparing powder graphene |
| CN112831108A (en) * | 2019-11-25 | 2021-05-25 | 北京石墨烯研究院 | Polyethylene-graphene composite material and preparation method thereof |
| CN113718364A (en) * | 2021-08-24 | 2021-11-30 | 南通强生石墨烯科技有限公司 | Graphene high-strength impact-resistant aramid fiber and preparation method thereof |
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013011250A1 (en) * | 2011-07-21 | 2013-01-24 | Arkema France | Graphene-based conductive composite fibres |
| KR20150066180A (en) * | 2013-12-06 | 2015-06-16 | 코오롱인더스트리 주식회사 | Method of manufacturing aramid fiber with excellent tenacity and aramid fiber manufactured thereby |
| CN106835332A (en) * | 2016-09-14 | 2017-06-13 | 济南圣泉集团股份有限公司 | Compound para-aramid fiber of high performance Graphene and preparation method thereof, application |
| CN106498538A (en) * | 2016-11-18 | 2017-03-15 | 株洲时代新材料科技股份有限公司 | The preparation method and applications of high-termal conductivity aromatic polyamide fibre |
| WO2018166477A1 (en) * | 2017-03-15 | 2018-09-20 | 山东圣泉新材料股份有限公司 | Modified fibre product, preparation method therefor and use thereof |
| CN109056098A (en) * | 2018-08-07 | 2018-12-21 | 李解 | A kind of preparation method of high performance graphene aramid fiber and thus obtained high performance graphene aramid fiber |
| CN110451496A (en) * | 2019-09-17 | 2019-11-15 | 北京石墨烯研究院 | A method of continuously high-volume preparing powder graphene |
| CN112831108A (en) * | 2019-11-25 | 2021-05-25 | 北京石墨烯研究院 | Polyethylene-graphene composite material and preparation method thereof |
| CN113718364A (en) * | 2021-08-24 | 2021-11-30 | 南通强生石墨烯科技有限公司 | Graphene high-strength impact-resistant aramid fiber and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117385488A (en) * | 2023-12-12 | 2024-01-12 | 电子科技大学 | Flame-retardant and strength-enhanced graphene modified aramid fiber and preparation method thereof |
| CN117385488B (en) * | 2023-12-12 | 2024-03-12 | 电子科技大学 | Flame-retardant and strength-enhanced graphene modified aramid fiber and preparation method thereof |
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