CN103015157A - Method for improving tensile strength of carbon fiber by utilizing graphene - Google Patents
Method for improving tensile strength of carbon fiber by utilizing graphene Download PDFInfo
- Publication number
- CN103015157A CN103015157A CN2012105067494A CN201210506749A CN103015157A CN 103015157 A CN103015157 A CN 103015157A CN 2012105067494 A CN2012105067494 A CN 2012105067494A CN 201210506749 A CN201210506749 A CN 201210506749A CN 103015157 A CN103015157 A CN 103015157A
- Authority
- CN
- China
- Prior art keywords
- graphene
- carbon fiber
- deposition
- corona discharge
- suspension
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 106
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 106
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 97
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 238000000034 method Methods 0.000 title claims abstract description 39
- 239000000725 suspension Substances 0.000 claims abstract description 24
- 238000000151 deposition Methods 0.000 claims abstract description 17
- 230000008021 deposition Effects 0.000 claims abstract description 17
- 238000003851 corona treatment Methods 0.000 claims abstract description 9
- 238000005274 electrospray deposition Methods 0.000 claims abstract description 9
- 239000002608 ionic liquid Substances 0.000 claims abstract description 9
- 239000002270 dispersing agent Substances 0.000 claims abstract description 6
- 239000012153 distilled water Substances 0.000 claims abstract description 4
- 230000005611 electricity Effects 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 3
- 239000011261 inert gas Substances 0.000 claims abstract description 3
- 208000028659 discharge Diseases 0.000 claims abstract 7
- VOQMXOIALAHYNN-UHFFFAOYSA-N benzenesulfonate;1h-imidazol-1-ium Chemical compound [NH2+]1C=CN=C1.[O-]S(=O)(=O)C1=CC=CC=C1 VOQMXOIALAHYNN-UHFFFAOYSA-N 0.000 claims abstract 2
- 239000007943 implant Substances 0.000 claims abstract 2
- 230000008569 process Effects 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000002356 single layer Substances 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 6
- 230000008439 repair process Effects 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 3
- 238000000889 atomisation Methods 0.000 claims description 2
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 claims description 2
- 238000004070 electrodeposition Methods 0.000 claims description 2
- 230000007547 defect Effects 0.000 claims 3
- 238000004924 electrostatic deposition Methods 0.000 claims 3
- 125000000101 thioether group Chemical group 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 5
- 230000003068 static effect Effects 0.000 abstract description 3
- 230000007847 structural defect Effects 0.000 abstract 2
- 238000005507 spraying Methods 0.000 abstract 1
- 238000010276 construction Methods 0.000 description 22
- 230000000694 effects Effects 0.000 description 15
- 230000002950 deficient Effects 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 9
- 208000037656 Respiratory Sounds Diseases 0.000 description 8
- 238000007306 functionalization reaction Methods 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 7
- 239000000835 fiber Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 4
- 238000005367 electrostatic precipitation Methods 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 208000002925 dental caries Diseases 0.000 description 3
- 230000005021 gait Effects 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- -1 imidazoles benzene sulfonate Chemical class 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 238000004062 sedimentation Methods 0.000 description 3
- 238000009987 spinning Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000005576 amination reaction Methods 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 230000000640 hydroxylating effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000002109 single walled nanotube Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000009718 spray deposition Methods 0.000 description 2
- 229950004288 tosilate Drugs 0.000 description 2
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 description 1
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical group C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000004026 adhesive bonding Methods 0.000 description 1
- 239000011157 advanced composite material Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 230000000386 athletic effect Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000005255 carburizing Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 230000009514 concussion Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 230000005686 electrostatic field Effects 0.000 description 1
- 238000007590 electrostatic spraying Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 230000002040 relaxant effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Landscapes
- Chemical Or Physical Treatment Of Fibers (AREA)
- Inorganic Fibers (AREA)
Abstract
一种石墨烯提高碳纤维抗拉强度的方法，采用改进电雾化沉积法将石墨烯植入于碳纤维的表面结构缺陷进而增加其强度，包括：1)将预氧化、炭化后的碳纤维束传送至高压电晕放电区在-5～-30kV高压电下进行电晕放电处理，行进速度5～30m/h，使碳纤维表面结构缺陷中带上一定量的负电荷；2)将石墨烯与蒸馏水和少许分散剂配制成均一稳定悬浮液，石墨烯为功能化石墨烯，取自氨基化、磺酸化或羟基化石墨烯中的一种，分散剂为咪唑类苯磺酸盐离子液体中的一种；3)石墨烯悬浮液施加20～50kV的正极静电，带电碳纤维束平展且接地构成喷涂液接受体，遂通过电雾化沉积将石墨烯植入碳纤维表面结构缺陷内，以碳纤维与石墨烯的重量比计，沉积量控制为1000∶(0.1～4)；4)经石墨烯雾化沉积后碳纤维束在300～1600℃惰性气体氩气气氛下进行热处理。碳纤维抗拉强度可提高130％以上。
A method for graphene to improve the tensile strength of carbon fibers, using improved electrospray deposition to implant graphene into the surface structural defects of carbon fibers to increase its strength, including: 1) transferring pre-oxidized and carbonized carbon fiber bundles to high The piezoelectric corona discharge area is subjected to corona discharge treatment under high voltage of -5 ~ -30kV, and the travel speed is 5 ~ 30m/h, so that a certain amount of negative charge is carried on the surface structural defects of carbon fibers; 2) the graphene and distilled water Prepare a uniform and stable suspension with a small amount of dispersant. Graphene is functionalized graphene, which is one of aminated, sulfonated or hydroxylated graphene. The dispersant is one of imidazole benzenesulfonate ionic liquids. 3) 20-50kV positive static electricity is applied to the graphene suspension, and the charged carbon fiber bundles are flattened and grounded to form a spraying liquid acceptor. In terms of weight ratio, the deposition amount is controlled to be 1000:(0.1-4); 4) After atomized graphene deposition, the carbon fiber bundle is heat-treated at 300-1600° C. under an inert gas argon atmosphere. The tensile strength of carbon fiber can be increased by more than 130%.
Description
Technical field
The present invention relates to the method that a kind of Graphene improves tensile strength of carbon fibers, particularly adopt the method that the electrospray sedimentation is repaired the carbon fiber surface fault of construction with Graphene and then improved tensile strength of carbon fibers of improving.
Background technology
Carbon fiber almost can be considered to up to now specific strength and the highest nonmetallic materials of specific modulus, except the mechanical property of excellence, it also has other multiple premium properties concurrently,, resist chemical high temperature resistant such as low-density, low resistance, high thermal conductance, low-thermal-expansion, radiation hardness etc., become the reinforcing material of the indispensable advanced composite material of aerospace field, also had wide practical use in fields such as communications and transportation, the energy, athletic sports appliance, civil construction.Yet in fact the intensity of existing carbon fiber product and elastic modelling quantity exist very large gap with theoretical value, take TENSILE STRENGTH as example, only are 3～5% of theoretical value generally.The basic reason that causes this phenomenon is carbon fiber ubiquity fault of construction, carbon fiber such as acrylonitrile group prepares with solution spinning because of its precursor especially, fiber is followed the effusion of solvent in solidification forming, the carbon fiber structural defective that finally makes is particularly serious.The fault of construction of carbon fiber comprises internal flaw (such as the cavity) and blemish (such as depression and crackle), and blemish is the principal element that causes intensity to descend, its weight even can reach 90%.
In the prior art, people more pass through to improve former yarn quality, improve pre-oxidation and carbonization technique etc. in the hope of the formation of minimizing fault of construction, but produce little effect with regard to the improvement ratio of carbon fiber product intensity actual value and theoretical value gap." Nanotube composite carbon fibers " [" Applied Physics Letters " 1999,75 (7), P1329～1334] literary composition discloses a kind of co-blended spinning method that adopts Single Walled Carbon Nanotube sneaked into the method that precursor prepares asphalt base carbon fiber, to improve mechanical property and the electrical property of carbon fiber, it is said that the asphaltic base carbon fiber reinforce plastic TENSILE STRENGTH and the elastic modelling quantity that contain the 5wt.% Single Walled Carbon Nanotube have improved respectively 90% and 150%.Yet the method has mainly remedied carbon fiber internal structure defective, the Surface Structures defective remedy the effect limited.In addition, the surface energy of CNT is very big, be scattered in equably in the spinning solution by no means easyly, uses so be difficult to realize large-scale industrialization.The in addition also trial of visible " later stage reparation " discloses a kind of manufacture method of high-strength carbon fiber such as Chinese patent application 03137023.3, and it is with CH
4Pass into plasma generator with Ar with certain proportioning, satisfy carbon fiber by the plasma high-temperature district, carry out the graphited while at carbon fiber, methane cracking under the effect of high-temperature electric arc plasma produces the carburizing of ion carbon to carbon fiber surface and inside, thereby remedies its fault of construction.The good news is that very it is stronger to the specific aim of carbon fiber surface fault of construction reparation, but " reparation " efficient of obvious this method is not ideal enough, the cost of industrial applications can be higher.Cheng Bowen etc. disclose the intensity that a kind of method that adopts the electrostatic spraying CNT increases carbon fiber in Chinese patent application numbers 201010211436.7,201010211437.1,201010211410.2 etc., the method technique is simple, and carbon fiber strength improves more than 100%.But this technology Shortcomings is: the CNT yardstick is relatively large, although its diameter several to tens nanometers, but its length range is between several microns to tens microns, far above carbon fiber surface fault of construction size (about tens between the hundreds of nanometer), easy like this causing in the surface texture defective that only has the part CNT to enter carbon fiber in the electrostatic spray process (radially injecting), most CNTs cover carbon fiber surface; In addition, because the draw ratio of CNT is large, in electrostatic spray process, can mutually tangle between the CNT and agglomerating, affect jeting effect.
Summary of the invention
The invention provides the method that a kind of Graphene improves tensile strength of carbon fibers, it repairs the carbon fiber surface fault of construction after having adopted Graphene, and then increases the intensity of carbon fiber.Effect and efficient are all very good, are suitable for industrializing implementation, have solved preferably the technical problem that prior art exists.
Below be the concrete technical scheme of the present invention:
A kind of Graphene improves the method for tensile strength of carbon fibers, and it adopts improvement electrospray sedimentation that Graphene is implanted in the surface texture defective of carbon fiber and then increases its intensity.The method comprises following process:
1) carbon fiber Corona discharge Treatment: the carbon fiber bundle 1 after pre-oxidation, the charing is sent to the high-voltage corona discharge district by conveyer belt 6 carries out Corona discharge Treatment, corona discharge assembly comprises that high voltage source 2, point discharge device 3 and grounding electrode plate 4 form, wherein high voltage source 2 is the negative electricity generator, its negative pole links to each other with point discharge device 3 by wire 21, and is anodal by wire 22 ground connection; By the gait of march 5～30m/h of control conveyer belt 6, the corona voltage of high voltage source 2-5～-30kV, arcing distance (point discharge device 3 and grounding electrode plate 4 spacings) is 1～5cm;
2) graphene suspension configuration: Graphene is mixed with stable homogeneous suspension with solvent and a little dispersant, Graphene is functionalization graphene, take from a kind of in amination, the sulfonated or hydroxylating Graphene, the content of functionalization group is 0.5～4wt.%, solvent is distilled water, dispersant is a kind of in the imidazoles benzene sulfonate ionic liquid, and wherein the content of ionic liquid is 0.1～1wt.%, and the content of Graphene is 10～60g/L in the suspension;
3) electrostatic precipitation Graphene: the carbon fiber bundle 1 through Corona discharge Treatment enters the electrostatic precipitation district through conveyer belt 6 with identical speed, the electrostatic precipitation device is comprised of high voltage source 7, spininess injector 9 and grounding electrode plate 4 ', high voltage source 7 is positive electric generator, its anodal wire 71 that passes through links to each other with spininess injector 9, and negative pole is by wire 72 ground connection; Graphene suspension is delivered to spininess injector 9 cavitys that are positioned at directly over the carbon fiber 1 through conduit 8, high voltage source 7 applies voltage 20～50kV and forms the electro-deposition district with grounding electrode plate 4 ', carbon fibre tow 1 lies on conveyer belt 6 and consists of acceptor, graphene suspension in spininess injector 9 cavitys in the surface texture defective, obtains Graphene and repairs carbon fiber in carbon fiber surface in high-pressure electrostatic atomizing deposit; Deposition distance (distance between injector syringe needle and the carbon fiber bundle) is controlled to be 5～30cm, and in the weight ratio of carbon fiber and Graphene, the deposition of Graphene is controlled to be 1000 in the carbon fiber surface fault of construction: (0.1～4);
4) Graphene is repaired carbon fiber heat treatment: carbon fiber bundle is delivered in the annealing device 11 with identical speed behind the Graphene spray deposition, heat-treats 300～1600 ℃ of heat treatment temperatures under inert gas argon gas atmosphere.
Said process 1) is actually at carbon fiber surface and introduces as a result some negative electrical charges in the defective, will help like this to be implanted in the carbon fiber surface fault of construction with the Graphene orientation of positive charge, but not be deposited on the surface of carbon fiber.Its basic principle is: under the high-pressure electrostatic effect, pin termination electrode 3 changes into air pole just, negative two kinds of electric charges, the positive charge opposite with electrode moves towards the needlepoint electrode end, and the negative electrical charge identical with polarity of electrode is deposited on the surface of carbon fiber and carbon fiber, because the carbon fiber guiding electrical property is better, the electric charge that is deposited on carbon fiber surface forms easily the conductive channel loss and disappears, but the electric charge in the defective is difficult to be formed the loss passage and resides in the fault of construction, thus reside in the fault of construction the negative electrical charge electric charge will with electrospray deposition process subsequently in attract each other so that in the easier surface texture defective that enters carbon fiber of Graphene with the Graphene of positive charge.Preferred 10～the 20m/h of gait of march of the conveyer belt 6 described in this process, the corona voltage of described high voltage source 2-20～-25kV, described arcing distance is 2～3cm.This process can Effective Regulation electrospray deposition process in the directed movement of particle, it is better to compare traditional electrical spray deposition implementation result.
Said process 2) described functionalization graphene can be functionalized single layer graphite alkene and/or functionalization multi-layer graphene, and diameter is generally 0.1～5 μ m, and thickness is 0.34～3.4nm; The functionalization group content of described functionalized carbon nano-tube is preferably 3～4wt.%; Described ionic liquid is preferably 1-butyl-3-methylimidazole tosilate or 1,3-methylimidazole tosilate; The content of described suspension intermediate ion liquid is preferably 0.4～0.6 volume %; The content of Graphene is preferably 30～40g/L in the described suspension.
Said process 3) described spininess injector 9 preferably applies the anodal static of 30～40kV; Described deposition distance preferably is controlled to be 15～25cm; The deposition of CNT preferably is controlled to be 1000 in the described carbon fiber surface fault of construction: (1.5～2.5).
Said process 4) effect is to make carbon fiber and Graphene at the interface, and the active atoms of carbon of Graphene active atoms of carbon in the carbon fiber surface fault of construction is combined, so that form covalent bonds between carbon fiber and Graphene, and to improve the carbon fiber mechanical property; When treatment temperature enough high, except above-mentioned covalent bonds occurs, carbon fiber structural changes the higher graphite-structure of degree of crystallinity into from random graphits structure, crystallization will occur between turbostratic graphite and the lamellar graphite alkene to reset simultaneously, whole process comprises the processes such as the eliminating, multinuclear aromatic ring plane structural organization, crystallite rearrangement, little product merging of non-carbon atom, will can further improve tensile strength of carbon fibers and modulus like this.But consider that temperature is higher, equipment requirement is also strict, and processing cost will significantly increase, preferred 1000～1300 ℃ of the heat treatment temperature described in the present invention.
One of key problem in technology of the present invention is that this desirable sheet high-carbon material of selection Graphene is implemented the reparation to the carbon fiber surface fault of construction.It is generally acknowledged when carbon fiber is subject to External Force Acting, the easiest breakaway poing that becomes fiber of the crackle of fiber surface, under external force, the tip of crackle will produce stress and concentrate, owing to lack plastic deformation, the stress of concentrating is difficult for relaxing and discharges, and can only form new surface with crackle bamboo telegraph and expansion, finally causes the carbon fiber fracture.The lamellar spacing of Graphene is nanoscale (a few nanometer), and far below the carbon fiber surface crack size, under electrostatic atomization deposition electric field action, Graphene is very easy to be filled in the crackle.Specific area is large, surface energy is high, surface atom proportion high because Graphene has, intermolecular force between Graphene and Graphene, Graphene and the carbon fiber (Van der Waals force) is high, particularly after heat treatment also has covalent bond between the carbon atom in Graphene and the carbon fiber structural defective.For this reason, the load of carbon fiber crackle one side after the Graphene reparation can be fast be passed to the opposite side of crackle by being filled in Graphene in the crackle, and then stress that can the establishment cracks concentrates, and realizes that its tensile strength improves.
Yet, just because the surface energy of Graphene is larger, very easily gather, thus Graphene before the electrospray deposition self Uniform Dispersion and orientated deposition to be implanted in the carbon fiber surface fault of construction be the prerequisite that reaches above-mentioned desirable reparation state necessity.Another key problem in technology of the present invention is to utilize dexterously the improvement electrospray to deposit this technological means, and determines suitable sedimentary condition as the basis take a large amount of experiments, thereby has successfully realized above-mentioned target.After the suspension that contains Graphene has applied high-voltage positive electrode static, because of Graphene band like charges, thereby mutually repel and be vaporific dispersion with dispersion liquid, the at this moment volatilization of solvent, the positively charged Graphene of separating out is directed the implantation in the carbon fiber surface fault of construction under the effect of electrostatic field force.Suitable deposition is very important, the very few effect that is difficult to manifest enhancing, and the excessive humidification that then can not give play to Graphene fully increases cost.
The suspension of Graphene adopts a kind of aqueous solution of ionic liquid, and with respect to the dispersion in organic solvent that routine is used, it is better that it has dispersion effect, little to the pollution of environment, more the characteristics such as environmental protection.
Graphene adopts the surface-functionalized Graphenes such as amination, sulfonated or hydroxylating, after the Graphene surface is with these functionalization groups, its surface polarity greatly strengthens, and suspension is the ionic liquid aqueous solution of polarity, and this is so that Graphene has better dispersiveness in suspension.With respect to the CNT of non-functionalization, the active force of functionalized carbon nano-tube and carbon fiber surface also strengthens to some extent.
Although the thickness of single or multiple lift Graphene is different, but its difference still belongs to very small for the size of carbon fiber surface fault of construction after all, simultaneously this species diversity is unlikely to cause the condition of repair process to change to some extent, so no matter the Graphene of single or multiple lift uses separately or both use with the mixing of any ratio and all do not affect realization of the present invention.Just because the active atoms of carbon of single-layer graphene is more, and is easier to tangle and produces more network node, experimental data shows that the usage ratio when single-layer graphene increases, and strengthening effect can improve thereupon.
The tensile strength of carbon fiber can improve more than 130% after the Graphene reparation of the present invention, and has the advantages such as technique is simple, the Graphene consumption is few, cost is low, efficient is high, the repairing effect of carbon fiber surface fault of construction is good, is easy to realize industrial applications.
Description of drawings
Fig. 1 is that the present invention adopts improvement electrospray sedimentation that Graphene is implanted carbon fiber surface fault of construction schematic diagram.
The below will the invention will be further described by specific embodiment.
The specific embodiment
[embodiment 1～7]
(1) carbon fiber Corona discharge Treatment
Adopt self-control to test without the PAN base carbon fibre of gluing, the specification of carbon fiber is: 3K, single fiber average diameter 7.0 μ m.Carbon fibre tow 1 is launched, and be tiled in stainless conveyer belt 6 and deliver to the high-voltage corona discharge district and carry out Corona discharge Treatment, by controlling the gait of march of suitable conveyer belt 6, the corona voltage of high voltage source 2, the arcing distance of point discharge device 3 and grounding electrode plate 4.The corona discharge process condition of each embodiment sees Table 1.
(2) graphene suspension preparation
Getting commercially available functionalization graphene places container to mix with the dispersion liquid that is mixed with by distilled water and a small amount of ionic liquid in required ratio, then proportion is that the ultrasonic wave of 20kHz carries out ultrasonic concussion, continue about 30min, Graphene is fully disperseed in dispersion liquid, and the suspension that then is mixed with desired concn is for subsequent use.The suspension composition of each embodiment sees Table 2, and the single-layer graphene thickness distribution that adopts is 0.34nm, and the multi-layer graphene thickness distribution is 0.68～6.8nm, and the two diameter distributes and is 0.1～5 μ m.
(3) electrospray deposition Graphene
Carbon fiber bundle 1 through Corona discharge Treatment is delivered to the electrostatic precipitation district through conveyer belt 6 with phase same rate (seeing Table 1), the graphene suspension of above-described embodiment 1～7 preparation through conduit 8 be delivered to be positioned at directly over the carbon fiber 1 and with high voltage source 7 anodal spininess injector 9 cavitys that link to each other, and outpoured with 10ml/h by the every hole of metal kernel small needle tube, the capillary needle bobbin is close to be 100 pin/rice
2, pinhole diameter is 0.8mm.At this moment, by applying a suitable voltage in high voltage source 7, graphene suspension drops in the atomizing of high-pressure electrostatic effect lower moment, this moment Graphene along with the aqueous solvent evaporation under electric field action orientation be implanted in the carbon fiber surface fault of construction, obtain Graphene and repair carbon fiber; Apply voltage, deposition distance, deposition and control repairing effect by changing HV generator 7.The electrospray deposition parameter of each embodiment sees Table 3.
(4) Graphene is repaired carbon fiber heat treatment
Carbon fiber bundle after the Graphene reparation is entered with identical speed in the annealing device 11 of argon atmosphere in uniform temperature heat treatment, to process zone distance be 6m to available heat in the treating apparatus.Control thermal effectiveness by the control heat treatment temperature.The electrospray deposition parameter of each embodiment sees Table 3.
Measure TENSILE STRENGTH and the tensile strength calculated increase rate of carbon fiber before and after the CNT deposition, the results are shown in Table 3.
Table 1 carbon fiber electrically corona embodiment technological parameter
Table 2 suspension configuration embodiment
* the weight ratio of single-layer graphene and multi-layer graphene is 1: 2.
Each embodiment electrospray deposition of table 3, Technology for Heating Processing and effect
Annotate: 1) weight ratio of deposition is carbon fiber: Graphene;
2) TENSILE STRENGTH I, TENSILE STRENGTH II are respectively the TENSILE STRENGTH of carbon fiber before and after the CNT deposition;
3) TENSILE STRENGTH increase rate=[(TENSILE STRENGTH II-TENSILE STRENGTH I)/TENSILE STRENGTH I] * 100%.
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012105067494A CN103015157A (en) | 2012-12-03 | 2012-12-03 | Method for improving tensile strength of carbon fiber by utilizing graphene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012105067494A CN103015157A (en) | 2012-12-03 | 2012-12-03 | Method for improving tensile strength of carbon fiber by utilizing graphene |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103015157A true CN103015157A (en) | 2013-04-03 |
Family
ID=47964222
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012105067494A Pending CN103015157A (en) | 2012-12-03 | 2012-12-03 | Method for improving tensile strength of carbon fiber by utilizing graphene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103015157A (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103243544A (en) * | 2013-05-07 | 2013-08-14 | 中国科学院山西煤炭化学研究所 | Method for modifying carbon fiber surface |
| EP3040371A1 (en) * | 2015-01-05 | 2016-07-06 | The Boeing Company | Graphene-augmented carbon fiber for aerospace composites |
| US9421739B2 (en) | 2015-01-05 | 2016-08-23 | The Boeing Company | Graphene aerospace composites |
| US9518160B2 (en) | 2015-01-05 | 2016-12-13 | The Boeing Company | Graphene-augmented composite materials |
| CN104629069B (en) * | 2013-11-11 | 2017-10-31 | 北京化工大学 | A kind of preparation of insulating barrier enveloped carbon nanometer tube orientation absorption carbon fiber prepreg |
| US10266677B2 (en) | 2015-01-05 | 2019-04-23 | The Boeing Company | Graphene-augmented composite materials |
| CN111364166A (en) * | 2020-03-16 | 2020-07-03 | 厦门大学 | A kind of preparation method of surface function synchronously modified flexible nanofiber composite membrane |
| US10875986B2 (en) | 2015-01-05 | 2020-12-29 | The Boeing Company | Graphene fiber for aerospace composites |
| CN113863000A (en) * | 2021-11-01 | 2021-12-31 | 浙江莹隆纤维科技有限公司 | Preparation method of three-dimensional fluorescent graphene fiber |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4666736A (en) * | 1983-04-05 | 1987-05-19 | Director-General Of Agency Of Industrial Science And Technology | Highly electroconductive graphite continuous filament and process for preparation thereof |
| JPH07102473A (en) * | 1993-09-30 | 1995-04-18 | Toyobo Co Ltd | Production of polybenzazole fiber improved in adhesiveness |
| CN102296457A (en) * | 2010-06-25 | 2011-12-28 | 中国石油化工股份有限公司 | Method for improving strength of carbon fiber |
| CN102296461A (en) * | 2010-06-25 | 2011-12-28 | 中国石油化工股份有限公司 | Method for improving strength of carbon fiber |
| CN102296460A (en) * | 2010-06-25 | 2011-12-28 | 中国石油化工股份有限公司 | Method for enhancing carbon fiber |
-
2012
- 2012-12-03 CN CN2012105067494A patent/CN103015157A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4666736A (en) * | 1983-04-05 | 1987-05-19 | Director-General Of Agency Of Industrial Science And Technology | Highly electroconductive graphite continuous filament and process for preparation thereof |
| JPH07102473A (en) * | 1993-09-30 | 1995-04-18 | Toyobo Co Ltd | Production of polybenzazole fiber improved in adhesiveness |
| CN102296457A (en) * | 2010-06-25 | 2011-12-28 | 中国石油化工股份有限公司 | Method for improving strength of carbon fiber |
| CN102296461A (en) * | 2010-06-25 | 2011-12-28 | 中国石油化工股份有限公司 | Method for improving strength of carbon fiber |
| CN102296460A (en) * | 2010-06-25 | 2011-12-28 | 中国石油化工股份有限公司 | Method for enhancing carbon fiber |
Non-Patent Citations (2)
| Title |
|---|
| JINHAI GUO等: "《Continuous preparation of multiscale reinforcement by electrophoretic deposition of carbon nanotubes onto carbon fiber tows》", 《CARBON》 * |
| 郭金海: "《电泳沉积制备氧化石墨烯- 碳纤维杂化增强材料》", 《第17届全国复合材料学术会议论文》 * |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103243544A (en) * | 2013-05-07 | 2013-08-14 | 中国科学院山西煤炭化学研究所 | Method for modifying carbon fiber surface |
| CN103243544B (en) * | 2013-05-07 | 2015-09-02 | 中国科学院山西煤炭化学研究所 | A kind of method of modifying of carbon fiber surface |
| CN104629069B (en) * | 2013-11-11 | 2017-10-31 | 北京化工大学 | A kind of preparation of insulating barrier enveloped carbon nanometer tube orientation absorption carbon fiber prepreg |
| US9421739B2 (en) | 2015-01-05 | 2016-08-23 | The Boeing Company | Graphene aerospace composites |
| US9434826B2 (en) | 2015-01-05 | 2016-09-06 | The Boeing Company | Graphene-augmented carbon fiber for aerospace composites |
| US9518160B2 (en) | 2015-01-05 | 2016-12-13 | The Boeing Company | Graphene-augmented composite materials |
| EP3040371A1 (en) * | 2015-01-05 | 2016-07-06 | The Boeing Company | Graphene-augmented carbon fiber for aerospace composites |
| US9963562B2 (en) | 2015-01-05 | 2018-05-08 | The Boeing Company | Graphene-augmented composite materials |
| US10266677B2 (en) | 2015-01-05 | 2019-04-23 | The Boeing Company | Graphene-augmented composite materials |
| US10400075B2 (en) | 2015-01-05 | 2019-09-03 | The Boeing Company | Graphene-augmented composite materials |
| US10851215B2 (en) | 2015-01-05 | 2020-12-01 | The Boeing Company | Graphene-augmented composite materials |
| US10875986B2 (en) | 2015-01-05 | 2020-12-29 | The Boeing Company | Graphene fiber for aerospace composites |
| US11174371B2 (en) | 2015-01-05 | 2021-11-16 | The Boeing Company | Graphene-augmented composite materials |
| CN111364166A (en) * | 2020-03-16 | 2020-07-03 | 厦门大学 | A kind of preparation method of surface function synchronously modified flexible nanofiber composite membrane |
| CN113863000A (en) * | 2021-11-01 | 2021-12-31 | 浙江莹隆纤维科技有限公司 | Preparation method of three-dimensional fluorescent graphene fiber |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103015157A (en) | Method for improving tensile strength of carbon fiber by utilizing graphene | |
| CN103015156A (en) | Method for improving tensile strength of carbon fiber | |
| CN102296460A (en) | Method for enhancing carbon fiber | |
| CN102296457A (en) | Method for improving strength of carbon fiber | |
| CN103015152A (en) | Method for improving tensile strength of carbon fiber | |
| CN102296461A (en) | Method for improving strength of carbon fiber | |
| JP4207398B2 (en) | Method for manufacturing wiring of carbon nanotube structure, wiring of carbon nanotube structure, and carbon nanotube device using the same | |
| Yuan et al. | Improving fiber alignment during electrospinning | |
| Moon et al. | Strong electrospun nanometer-diameter polyacrylonitrile carbon fiber yarns | |
| Ishii et al. | A new electrospinning method to control the number and a diameter of uniaxially aligned polymer fibers | |
| Lu et al. | Functionally graded and self-assembled carbon nanofiber and boron nitride in nanopaper for electrical actuation of shape memory nanocomposites | |
| CN103015153A (en) | Technique for repairing surface structure defects of carbon fiber | |
| Huynh et al. | Electrical property enhancement by controlled percolation structure of carbon black in polymer-based nanocomposites via nanosecond pulsed electric field | |
| CN106567157B (en) | A kind of preparation method of graphene nanoribbon in-situ toughening carbon nanofiber | |
| CN102296456A (en) | Method for enhancing strength carbon fiber | |
| CN103276379A (en) | Method for preparing surface silver-plated electric-spinning fiber by using dopamine | |
| Liu et al. | Effects of carbon nanotube length on interfacial properties of carbon fiber reinforced thermoplastic composites | |
| Li et al. | Mechanical and electrical properties of the PA6/SWNTs nanofiber yarn by electrospinning | |
| Zhou et al. | Carbon nanofiber yarns fabricated from co-electrospun nanofibers | |
| Chen et al. | Large-scale fabrication of highly aligned poly (m-phenylene isophthalamide) nanofibers with robust mechanical strength | |
| CN105679555A (en) | Preparation method for three-dimensional aminated carbon nanotube array/stretchable textile fiber electrode material | |
| Takasaki et al. | Ultra-fine fibers produced by laser-electrospinning | |
| CN102296458A (en) | Method for enhancing carbon fiber | |
| Liu et al. | Multiscale structure construction by layer-by-layer self-assembly to modify the carbon fiber surface | |
| CN103015154A (en) | Method for improving tensile strength of carbon fiber by utilizing carbon nano tubes |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20130403 |