CN103015152A - Method for improving tensile strength of carbon fiber - Google Patents

Method for improving tensile strength of carbon fiber Download PDF

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Publication number
CN103015152A
CN103015152A CN2012105065751A CN201210506575A CN103015152A CN 103015152 A CN103015152 A CN 103015152A CN 2012105065751 A CN2012105065751 A CN 2012105065751A CN 201210506575 A CN201210506575 A CN 201210506575A CN 103015152 A CN103015152 A CN 103015152A
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carbon fiber
graphene
tensile strength
suspension
corona discharge
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程博闻
康卫民
李磊
赵义侠
蔡占军
庄旭品
夏磊
徐志伟
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Tianjin Polytechnic University
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Abstract

The invention relates to a method for improving the tensile strength of a carbon fiber. An improved electric atomization deposition method is adopted for planting graphene into the surface structure defects of the carbon fiber, so as to improve the strength of the carbon fiber. The method provided by the invention comprises the following steps of: 1) transmitting a pre-oxidized and carbonized carbon fiber bundle into a high-voltage corona discharge area, and carrying out corona discharge under a high voltage of minus 5kV to minus 30kV, wherein the advancing speed is 5-30m/h, so that a certain amount of negative charge is taken along in the surface structure defects of the carbon fiber; 2) preparing graphene, distilled water and a small amount of dispersing agent into a uniform and stable suspension, wherein functional graphene selected from single-layer graphene and multi-layer graphene is adopted, and the dispersing agent is one of imidazole benzene sulfonate ionic liquids; 3) applying positive static electricity of 20-50kV to the graphene suspension, flattening the charged carbon fiber bundle and grounding to form a spraying fluid acceptor, and then planting the graphene into the surface structure defects of the carbon fiber by virtue of electric atomization deposition, wherein deposit is controlled to be 1000:(0.1-4) in weight ratio of the carbon fiber to the graphene; and 4) carrying out heat treatment on the carbon fiber bundle under the insert gas argon atmosphere at the temperature of 300-1600 DEG C after atomization deposition is carried out by virtue of the graphene. The tensile strength of the carbon fiber can be improved by more than 110%.

Description

A kind of tensile strength of carbon fibers improvement method
Technical field
The present invention relates to a kind of tensile strength of carbon fibers improvement method, particularly adopt to improve the electrospray sedimentation Graphene is implanted carbon fiber surface remedying its fault of construction, and then improve the method for tensile strength of carbon fibers.
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 a kind of tensile strength of carbon fibers improvement method, it repairs the carbon fiber surface fault of construction after adopting Graphene, and then improves 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 carbon fiber strength improvement method, it adopts improvement electrospray sedimentation that Graphene is implanted in carbon fiber surface to remedy its surface texture defective.The method comprises:
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 suspension with dispersion liquid, dispersion liquid is the mixture of ionic liquid and water, wherein the content of ionic liquid is 0.1~1wt.%, ionic liquid takes from 1, a kind of in 3-methylimidazole tosilate, 1-butyl-3-methylimidazole tosilate, chlorination 1-octyl group-3-methylimidazole or the 5-bromo-2-Methyl-3-nitropyridine, 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 Graphene can be single-layer graphene and/or multi-layer graphene, and diameter is generally 0.1~5 μ m, and thickness is 0.34~3.4nm; 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 Graphene 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, crystallite 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 present invention has also selected a kind of dispersion liquid of desirable Graphene, and this is a kind of aqueous solution of ionic liquid.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.
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 110% 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 7.2 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 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 CNT applies, the results are shown in Table 3.
Table 1 carbon fiber electrically corona embodiment technological parameter
Figure BSA00000815443500061
Table 2 suspension configuration embodiment
Figure BSA00000815443500062
* 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 CNT applies;
3) TENSILE STRENGTH increase rate=[(TENSILE STRENGTH II-TENSILE STRENGTH I)/TENSILE STRENGTH I] * 100%.

Claims (3)

1. tensile strength of carbon fibers improvement method, its adopts and improves electrospray sedimentation Graphene is implanted in the surface texture defective of carbon fiber and then improves its intensity, it is characterized in that 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 is 1~5cm;
2) graphene suspension configuration: Graphene is mixed with stable homogeneous suspension with solvent and a little dispersant, the stone dispersant is a kind of in the imidazoles benzene sulfonate ionic liquid, 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; The deposition distance 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 speed 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.
2. tensile strength of carbon fibers improvement method according to claim 1 is characterized in that process 1) described corona voltage-20~-25kV, described arcing distance is 2~3cm, the preferred 10~20m/h of the translational speed of described conveyer belt 6.
3. tensile strength of carbon fibers improvement method according to claim 1, said process 2) described Graphene can be single-layer graphene and/or multi-layer graphene, and diameter is 0.1~5 μ m, and thickness is 0.34~3.4nm.
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Cited By (5)

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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
CN107032799A (en) * 2017-05-18 2017-08-11 成都新柯力化工科技有限公司 A kind of pantograph pan graphene reinforcing glass fiber and preparation method
CN110016728A (en) * 2018-01-08 2019-07-16 吉林吉盟腈纶有限公司 A kind of preparation method of polyacrylonitrile graphene fiber
CN112852214A (en) * 2021-03-11 2021-05-28 湖南智涂新材料有限公司 Adhesion promoting material and preparation method and application thereof
CN114932724A (en) * 2022-05-06 2022-08-23 山东大学 High-strength electromagnetic shielding fiber composite material and preparation method and application thereof

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CN112852214A (en) * 2021-03-11 2021-05-28 湖南智涂新材料有限公司 Adhesion promoting material and preparation method and application thereof
CN114932724A (en) * 2022-05-06 2022-08-23 山东大学 High-strength electromagnetic shielding fiber composite material and preparation method and application thereof

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Application publication date: 20130403