CN109763320A - A kind of technique that graphene film repairs carbon fiber surface hole and crackle - Google Patents
A kind of technique that graphene film repairs carbon fiber surface hole and crackle Download PDFInfo
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- CN109763320A CN109763320A CN201811580044.0A CN201811580044A CN109763320A CN 109763320 A CN109763320 A CN 109763320A CN 201811580044 A CN201811580044 A CN 201811580044A CN 109763320 A CN109763320 A CN 109763320A
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Abstract
A kind of technique that graphene film repairs carbon fiber surface hole and crackle, carbon fiber is cleaned first with aqueous solution of nitric acid, immerses in hydrogen peroxide solution, oxidation processes is carried out in ultrasonic instrument, carbon fiber surface is rinsed with deionized water, is put into baking oven and is toasted；Then baked carbon fiber is sent to horizontal chemical vapor deposition stove, vacuumize process is carried out to chemical vapor deposition stove, argon gas is passed through, is then turned on heating device and heats up；Argon gas is passed through again to anneal, it is continual to pull catch carbon fiber；Then argon gas is switched into methane and hydrogen is grown, it is continual to pull catch carbon fiber；Finally turn off hydrogen, cools down；It is then turned off methane, cool the temperature to room temperature or is maintained under 30~37 DEG C of temperature constant states；The present invention repairs defect of carbon fiber surface structure using graphene, and then improves the intensity of carbon fiber, and effect and efficiency are adapted to industrializing implementation.
Description
Technical field
The invention belongs to defect of carbon fiber surface structure recovery technique fields, and in particular to a kind of graphene film repairing carbon
The technique of fiber surface hole and crackle.
Background technique
Since carbon fiber has axial strength and modulus high, good without creep, fatigue durability, specific heat and electric conductivity are between non-gold
Belong between metal, the advantages that thermal expansion coefficient is small, good corrosion resistance, and the density of fiber is low, and X-ray transparent is good, by
It is carried out widely as the strengthening material of the fields such as aerospace, communications and transportation, the energy, sports, civil construction composite material
Research；But its specific surface area active is small, surface energy is low, and the binding force between carbon fiber and matrix is small, so that carbon fiber is compound
The shear strength and bending strength of material are very low；Also, the actual strength and elasticity modulus of the carbon fiber product of existing technical grade
The theoretical value of design is far not achieved, by taking mechanical performance as an example, general tensile strength, interlaminar shear strength etc. are only theoretical value respectively
5%-20% or so.The fault of construction of carbon fiber is the basic reason for causing fiber mechanical performance to decline, such as: acrylonitrile group
Carbon fibre precursor be to be prepared by solution spinning, precursor tends to have the spilling of solvent during solidification forming, from
And lead to carbon fiber structural defect.The fault of construction of carbon fiber mainly include internal flaw (hole) and surface defect (recess and
Crackle), and the reason of cause fiber mechanical performance to decline, 80% or more is from fiber surface structure defect.
Existing carbon fiber manufacturing enterprise is mainly to pass through improve strand quality, improve the pre-oxidation in carbon fibre manufacturing processes
Reduce the generation of carbon fiber structural defect with carbonization technique etc., but with regard to the mechanical performance of existing carbon fiber product still with design
There is very big gap in value."nanotube composite carbon fiber"["applied physics letters"
1999,75 (7), P1329~1334] this article by the way that single armed carbon nanotube is mixed into precursor prepares asphalt base carbon fiber, mainly more
Carbon fiber internal structural defects are mended, it is said that containing the compound carbon fiber tensile strength of asphaltic base and elasticity of 5% single armed carbon nanotube
Modulus has been respectively increased 90% and 150%, but this method Surface Structures defect to make up effect limited.In addition, carbon nanotube
Surface greatly can be homogeneously dispersed in by no means easy in spinning solution, therefore be difficult to realize large-scale industrialization application.Cause
This, " the later period reparation " of carbon fiber is also particularly important.Cheng Bowen etc. Chinese Patent Application No. 201010211436.7,
201010211437.1, carbon fiber is enhanced using a kind of method of electrostatic spraying carbon nanotube in 201010122410.2 etc.
Intensity, this method simple process, carbon fiber strength improve 100%；But due to the length range of carbon nanotube at several microns extremely
Between tens microns, it is much higher than defect of carbon fiber surface structure size (about tens between several hundred nanometers), thus in electrospray
The breadth that carbon nanotube enters the surface texture defect (radial to inject) of carbon fiber is restricted in the process, causes most carbon nanometers
Pipe is covered on carbon fiber surface；Further, since the major diameter of carbon nanotube is bigger, in electrostatic spray process, carbon nanotube is easy
It intertwine with each other agglomerating, influences jeting effect.
Summary of the invention
In order to overcome the disadvantages of the above prior art, the object of the present invention is to provide a kind of graphene films to repair carbon
The technique of fiber surface hole and crackle repairs defect of carbon fiber surface structure using graphene, and then improves the strong of carbon fiber
Degree, effect and efficiency are adapted to industrializing implementation.
In order to achieve the above object, the technical scheme adopted by the invention is as follows:
A kind of technique that graphene film repairs carbon fiber surface hole and crackle, comprising the following steps:
1) surface treatment of carbon fibers: cleaning carbon fiber using aqueous solution of nitric acid, and the carbon fiber cleaned is immersed
In hydrogen peroxide solution using deionized water configuration, oxidation processes are carried out in ultrasonic instrument；Deionized water is used after the completion of processing
Carbon fiber surface is rinsed, carbon fiber will have finally been rinsed and is put into baking oven and toasted；
2) temperature rise period: baked carbon fiber is sent by conveyer belt to horizontal chemical vapor deposition stove, to chemistry
Gaseous phase deposition stove carries out vacuumize process, when vacuum reaches 5 × 10-1When MPa, being passed through argon gas and opening maintenance pump makes horizontal chemistry
Level of vacuum in gaseous phase deposition stove maintains 5.6 × 10-1MPa is then turned on heating device and is increased with the speed of 34 DEG C/min
To 1000 DEG C~1020 DEG C, 1060 DEG C~1070 DEG C then are risen to 3.4 DEG C/min again；
3) annealing stage: keeping the temperature at 1060 DEG C~1070 DEG C, is passed through argon gas 30min and anneals；Annealed
Cheng Zhong, with frequency for 10 times/min, the power of 20N is continual to pull catch carbon fiber；
4) growth phase: argon gas is switched into methane and hydrogen, grows 60min；During the growth process, with frequency for 10
The power of secondary/min, 20N are continual to pull catch carbon fiber；
5) finally first turn off hydrogen, temperature is dropped to 100~105 DEG C with the speed of 106 DEG C/min；Methane is then turned off,
It cools the temperature to room temperature or is maintained under 30~37 DEG C of temperature constant states.
Aqueous solution of nitric acid concentration is 10~12mol/L in the step 1), and soaking temperature is 118~120 DEG C, when cleaning
Between be 10min, the weight ratio of aqueous solution of nitric acid and carbon fiber is 25:1；Deionized water configures the hydrogen peroxide solution of 5%-6%,
Ultrasonic oxidation handles 20min, and deionized water rinses 5min, and it is 2h that baking temperature, which is 120~125 DEG C of times,.
Argon flow is 100~105sccm in the step 2, step 3).
The flow of methane and hydrogen is respectively 100~105sccm, 8~10sccm in the step 4).
The invention has the benefit that
The defect pattern of carbon fiber surface is the physical basis of graphene growth, so the surface topography of fiber is to graphene
Growth it is extremely important.Cleaning is carried out by aqueous solution of nitric acid and ultrasound breaks-hydrogen peroxide Combined Treatment oxidized fibre control defect
Pattern.Facilitate the growth that carbon fiber defect goes out graphene.And after handling 30min by co-oxidation, continuous carbon fibre
The oxygen-containing functional groups content such as hydroxyl, the carboxyl on surface increases, and C-C group content reduces, so that surface active element content increases.
And then the bonding of carbon fiber and polyamide is improved, enhance the interlaminar shear strength of carbon fibre composite.The life of graphene
Length relates generally to following process, absorption and decomposition of (1) hydroxyl class carbon source in substrate；(2) surface carbon atom is to matrix phase
Interior dissolution and the diffusion in body phase；(3) carbon atom can be precipitated from the opposite surface of body in temperature-fall period；(4) carbon atom exists
The nucleation of matrix surface and secondary reconstruct generate graphene.Methane in the present invention occurs under 1000 DEG C or higher temperature
Pyrolysis, since surface carbon concentration is higher than body phase, this concentration gradient can promote a part of surface to decompose the carbon atom generated in high temperature
It is lower to be spread to intrinsic silicon, it pulls pulling and makees to facilitate carbon atom and internally spread.During cooling, carbon in the substrate molten
Xie Du decline, carbon just precipitate into the surface of substrate in the form of graphite, and preferentially go out to form core in turn in the defects of crystal boundary, step
Form graphene.
Under external force, stress produced by the tip of the crackle of carbon fiber surface is concentrated, due to carbon fiber poor plasticity,
The stress of concentration is not easy to mitigate and discharge, and can only be propagated and be extended rapidly with crackle, and then carbon fiber is caused to be broken.It overflows and is formed
Graphene with a thickness of nanoscale (several nanometers), carbon fiber surface crack size is far below, in addition pulling drawing effect graphene very
It is easy to be filled into crackle.Although the thickness of single-layer or multi-layer graphene is different, lacked relative to carbon fiber surface structure
Falling into size, it is very small, can not influence the variation of repair process conditional, therefore single-layer or multi-layer graphene can reach and repair
The purpose of multiple carbon fiber surface defect.The active atomic of single-layer graphene is more, it is easier to and it tangles and generates more network nodes,
Experimental data shows that the reinforcing effect of single-layer graphene is more preferable.
The features such as graphene has large specific surface area, and surface can be high, and surface atom proportion is high, therefore graphene and stone
Intermolecular force (Van der Waals force) high (after heat treatment graphene and carbon fiber between black alkene, graphene and carbon fiber
There is also covalent bonds between carbon atom in fault of construction).The load of carbon fiber crackle side after graphene is repaired can
It is transferred to the other side of crackle quickly through the graphene being filled in crackle, and then can effectively inhibit the stress collection of cracks
In, it realizes and improves fibre tensile strength.The tensile strength of carbon fiber can be improved 180% or more after the method for the present invention reparation, and have
Have the advantages that simple process, graphene dosage are few, at low cost, high-efficient, defect of carbon fiber surface structure repairing effect is good, adapts to
In industrial mass production.
Detailed description of the invention
Fig. 1 is the surface micro-structure of carbon fibre precursor of the embodiment of the present invention.
Fig. 2 is the surface micro-structure after carbon fiber of the embodiment of the present invention is repaired.
Specific embodiment
It elaborates with reference to the accompanying drawings and examples to the present invention.
Embodiment 1, a kind of technique that graphene film repairs carbon fiber surface hole and crackle, comprising the following steps:
1) surface treatment of carbon fibers: being tested using the domestic carbon fiber not glued, and the specification of carbon fiber is 3K, single fiber
Diameter is 7.2 microns；Carbon fiber is placed in the aqueous solution of nitric acid that concentration is 10mol/L and is impregnated, aqueous solution of nitric acid and carbon fiber
Weight ratio be 25:1,120 DEG C of soaking temperature, scavenging period 10min, then by the carbon fiber cleaned immerse using go from
In the hydrogen peroxide solution of sub- water configuration 5%, oxidation processes 20min is carried out in ultrasonic instrument；Deionized water is used after the completion of processing
Carbon fiber surface 5min is rinsed, carbon fiber will have finally been rinsed and is put into 120 DEG C of baking ovens and carry out baking 2h；
2) temperature rise period: baked carbon fiber is sent by conveyer belt to horizontal chemical vapor deposition stove, then right
Chemical vapor deposition stove carries out vacuumize process, when vacuum reaches 5 × 10-1When MPa, being passed through argon gas and opening maintenance pump makes chemistry
Level of vacuum in gaseous phase deposition stove maintains 5.6 × 10-1MPa is then turned on heating device and is increased with the speed of 34 DEG C/min
To 1000 DEG C, 1060 DEG C then are risen to 3.4 DEG C/min again；
3) annealing stage: keeping the temperature at 1060 DEG C, is passed through argon gas 30min and anneals；In annealing process, with frequency
Rate is 10 times/min, and the power of 20N is continual to pull catch carbon fiber；
4) growth phase: argon gas is switched into methane and hydrogen, grows 60min；During the growth process, with frequency for 10
The power of secondary/min, 20N are continual to pull catch carbon fiber；
5) finally first turn off hydrogen, temperature is dropped to 100-105 DEG C with the speed of 106 DEG C/min；It is then turned off methane, it will
Temperature is down to room temperature or is maintained under 30 DEG C of temperature constant states.
The present embodiment has the beneficial effect that referring to Figures 1 and 2 there is a small amount of microflute on the surface of carbon fibre precursor shown in Fig. 1
Crack defect, Fig. 2 are the carbon fiber surface pattern after repairing, it can be seen that graphene is embedded in carbon fiber surface, has repaired carbon fiber
Micro- side trench defect in dimension table face.
Although technical solution of the present invention is described above in conjunction with the embodiments, the invention is not limited to above-mentioned
Embodiment, the above embodiments are only schematical, directiveness, rather than restrictive.The ordinary skill of this field
Personnel are under the enlightenment of description of the invention, can be in the case where not departing from the range that the claims in the present invention are protected
A variety of forms is made, these belong to the column of protection of the invention.
Claims (4)
1. the technique of a kind of graphene film repairing carbon fiber surface hole and crackle, which comprises the following steps:
1) surface treatment of carbon fibers: cleaning carbon fiber using aqueous solution of nitric acid, and the carbon fiber cleaned is immersed and is utilized
In the hydrogen peroxide solution of deionized water configuration, oxidation processes are carried out in ultrasonic instrument；It is rinsed after the completion of processing with deionized water
Carbon fiber surface will finally rinse carbon fiber and be put into baking oven and toasted；
2) temperature rise period: baked carbon fiber is sent by conveyer belt to horizontal chemical vapor deposition stove, to chemical gaseous phase
Cvd furnace carries out vacuumize process, when vacuum reaches 5 × 10-1When MPa, being passed through argon gas and opening maintenance pump makes horizontal chemical gaseous phase
Level of vacuum in cvd furnace maintains 5.6 × 10-1MPa is then turned on heating device and is increased to the speed of 34 DEG C/min
1000~1020 DEG C, 1060 DEG C~1070 DEG C then are risen to 3.4 DEG C/min again；
3) annealing stage: keeping the temperature at 1060 DEG C~1070 DEG C, is passed through argon gas 30min and anneals；In annealing process,
With frequency for 10 times/min, the power of 20N is continual to pull catch carbon fiber；
4) growth phase: argon gas is switched into methane and hydrogen, grows 60min；During the growth process, with frequency be 10 times/
The power of min, 20N are continual to pull catch carbon fiber；
5) finally first turn off hydrogen, temperature is dropped to 100~105 DEG C with the speed of 106 DEG C/min；It is then turned off methane, it will be warm
Degree is down to room temperature or is maintained under 30~37 DEG C of temperature constant states.
2. the technique of a kind of graphene film repairing carbon fiber surface hole according to claim 1 and crackle, feature
Be: aqueous solution of nitric acid concentration is 10~12mol/L in the step 1), and soaking temperature is 118~120 DEG C, scavenging period
For 10min, the weight ratio of aqueous solution of nitric acid and carbon fiber is 25:1；The hydrogen peroxide solution of deionized water configuration 5~6%, super
Sound oxidation processes 20min, deionized water rinse 5min, and it is 2h that baking temperature, which is 120~125 DEG C of times,.
3. the technique of a kind of graphene film repairing carbon fiber surface hole according to claim 1 and crackle, feature
Be: argon flow is 100~105sccm in the step 2), step 3).
4. the technique of a kind of graphene film repairing carbon fiber surface hole according to claim 1 and crackle, feature
Be: the flow of methane and hydrogen is respectively 100~105sccm, 8~10sccm in the step 4).
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| CN1456717A (en) * | 2003-05-29 | 2003-11-19 | 中国科学院山西煤炭化学研究所 | Method and apparatus for preapring high strength and high modulus graphitized carbon fibers |
| CN101698975A (en) * | 2009-09-23 | 2010-04-28 | 北京航空航天大学 | Method for modifying carbonized pre-oxidized fiber preform interface by carbon nanotube |
| CN103015153A (en) * | 2012-12-03 | 2013-04-03 | 天津工业大学 | Technique for repairing surface structure defects of carbon fiber |
| CN106868469A (en) * | 2017-03-15 | 2017-06-20 | 山东大学 | A kind of method that non-metal catalyst in silicon substrate prepares Graphene |
| CN106927705A (en) * | 2017-02-13 | 2017-07-07 | 东南大学 | A kind of method in copper facing steel fiber surface controllable growth graphene coated film |
| CN108502873A (en) * | 2018-06-26 | 2018-09-07 | 中国科学院苏州纳米技术与纳米仿生研究所南昌研究院 | A kind of high quality, less defect, the preparation method of the uniform graphene of structure |
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- 2018-12-24 CN CN201811580044.0A patent/CN109763320B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1456717A (en) * | 2003-05-29 | 2003-11-19 | 中国科学院山西煤炭化学研究所 | Method and apparatus for preapring high strength and high modulus graphitized carbon fibers |
| CN101698975A (en) * | 2009-09-23 | 2010-04-28 | 北京航空航天大学 | Method for modifying carbonized pre-oxidized fiber preform interface by carbon nanotube |
| CN103015153A (en) * | 2012-12-03 | 2013-04-03 | 天津工业大学 | Technique for repairing surface structure defects of carbon fiber |
| CN106927705A (en) * | 2017-02-13 | 2017-07-07 | 东南大学 | A kind of method in copper facing steel fiber surface controllable growth graphene coated film |
| CN106868469A (en) * | 2017-03-15 | 2017-06-20 | 山东大学 | A kind of method that non-metal catalyst in silicon substrate prepares Graphene |
| CN108502873A (en) * | 2018-06-26 | 2018-09-07 | 中国科学院苏州纳米技术与纳米仿生研究所南昌研究院 | A kind of high quality, less defect, the preparation method of the uniform graphene of structure |
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