CN107629224A - The preparation method of double sizing agent modified carbon fiber reinforced epoxy based composites - Google Patents
The preparation method of double sizing agent modified carbon fiber reinforced epoxy based composites Download PDFInfo
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Abstract
The present invention relates to the preparation method of double sizing agent modified carbon fiber reinforced epoxy based composites, the preparation method mixes SiO using OA POSS2The multiple modification of sizing agent and CNT sizing agents, avoid the introducing of complicated chemical key, scion grafting modification has been carried out to carbon fiber surface, and modified carbon fiber reinforced epoxy based composites are obtained by vacuum assistant resin infused normal temperature cure, so that the cutting performance of composite improves 24%, its tensile property improves 29%, is above the mechanical property of thermosetting moulding process.
Description
Technical field
The invention belongs to composite material surface technical field of modification, and it is carbon fiber reinforced epoxy resin-based multiple to be related to hybrid modification
The preparation method of condensation material, in particular, it is related to a kind of double sizing agent modified carbon fiber reinforced epoxy based composites
The probing into of preparation method, the preparation of carbon fiber reinforced epoxy resin-based composite, the detection of mechanical property.
Background technology
Carbon fiber reinforced epoxy resin-based composite is because of its light weight, intensity height is widely used in Aero-Space, builds
Build, the field such as auto industry, be the emphasis of high strength industrial product development and application.Therefore, the high-strength of carbon fiber how is ensured
The stretching of degree and solution carbon fiber, impact failure lamination problem are the problems faced at present.In the prior art, in order to carry
The inter-layer bonding force of high carbon fiber, usually using the modifies method of carbon fiber modifying or epoxy resin-matrix.Change for two kinds
For property method, the modifies mechanical property that can improve matrix of epoxy resin-matrix, it can also improve carbon fiber to a certain extent
The binding ability at interface between resin matrix, but the chemical bonds between modified matrix carbon fiber are weaker, and
And the original epoxy base unit weight of matrix is changed, therefore, the combination principle of the two is increasingly complex, comparatively more difficult control.Carbon is fine
Dimension is modified to have purpose, and selection is easy to the substance modification combined with epoxy radicals, and modifying process is more easy to control, and what be presently, there are changes
Property method have the kinds of processes such as chemical infiltration, plating, vapour deposition, plasma deposition, wherein chemical infiltrate because its cost is low, anti-
The advantages that answering liquid disposable is widely used.Among presently described research, the method being modified on surface has a lot,
Scholar's once being modified to epoxy resin-base using CNT so that the toughness of matrix has obtained a certain degree of raising；And
In terms of mixing organic-inorganic modified preparation, once with organic material and inorganic material it is mixed and modified after reapply composite wood
On material, this method causes the mixed and modified increase that can cause defect, so as to cause the lifting of the performance of composite little.And
For the composite of multicomponent modified carbon fiber, CN102912626A has ever done similar research with CN104277421A,
But because be the application of thermosetting moulding process, and there is no the method using sizing agent infiltration in modified technique, it is directly logical
Cross the chemical treating processes such as acid oxidase to be modified, modified is sufficiently complete, and the physics of graft is produced with chemical property
Certain influence, and carbon fiber belongs to different chemical systems from half siloxanes, the chemical functional groups effect between material
Good interface cohesion effect can not be realized, although the effect of the Various Complex such as chemical bond, Van der Waals force chemical bond effectively improves
Composite tensile strength and strain property, but bent toughness to composite, impact resistance generate unfavorable shadow
Ring.
The content of the invention
In view of analyzing above, it is an object of the invention to provide a kind of double sizing agent modified carbon fiber reinforced epoxy bases
The preparation method of composite.The preparation method mixes SiO using OA-POSS2The multiple modification of sizing agent and CNT sizing agents,
The introducing of complicated chemical key is avoided, scion grafting modification has been carried out to carbon fiber surface, and pass through vacuum assistant resin infused normal temperature
Solidification obtains modified carbon fiber reinforced epoxy based composites so that and the cutting performance of composite improves 24%, its
Tensile property improves 29%, is above the mechanical property of thermosetting moulding process.
To realize the purpose of the present invention, the invention provides a kind of double sizing agent modified carbon fiber reinforced epoxy bases to answer
The preparation method of condensation material, it is the step of this method：
1) carbon nano-tube modification solution is prepared：Silane coupler is dissolved in ethanol solution, stirring obtains silane coupled
Agent colloidal sol；Then silane coupler colloidal sol, amino multi-walled carbon nanotube are added separately in dispersant, in rotating speed 800-
Carbon nano-tube modification solution is uniformly mixing to obtain under 2000r/min；The quality hundred of each material in the carbon nano-tube modification solution
Point ratio is：0.1-0.8% silane couplers colloidal sol, 0.5-2.0% amino multi-walled carbon nanotube, 97.2%-99.4% dispersants；
2) carbon fiber surface pre-processes：Carbon cloth is immersed in cleaner and carries out surface clean, after then cleaning
Carbon cloth be dried and high temperature oxidation process, the high-temperature oxydation temperature is 300-600 DEG C, and the high-temperature oxydation time is
10-60min；Carbon cloth after oxidation processes is cooled to normal temperature, is placed in sample bag；
3) modification of carbon fiber：The pretreated carbon cloth of step 2) is immersed in carbon nano-tube modification solution
In, carbon cloth is taken out after ultrasonic vibration 50-90s, and be dried at normal temperatures；Then carbon cloth is placed on full of argon
In the tube furnace of gas, 2-5h is sintered at 600-900 DEG C, after being cooled to normal temperature, argon gas is closed, takes out sample；
4) twice-modified sizing agent is prepared：The SiO that particle diameter is 20nm-1 μm is prepared by raw material of tetraethyl orthosilicate2Powder；
Then by octa-aminopropyl polyhedral oligomeric silsesquioxane (OA-POSS) and SiO2Powder is dissolved in distilled water, and octa-aminopropyl is more
Face body oligomeric silsesquioxane (OA-POSS), SiO2The mass percent of powder and distilled water is 0.5%：0.5-1.0%：
98.5-99.0%；Under conditions of bath temperature is 60-100 DEG C, rotating speed is 500-1500r/min, stir to after being thoroughly mixed
Stop heating, standing arrives room temperature, obtains required twice-modified sizing agent；
5) the twice-modified processing of carbon fiber：It will be infiltrated through the sample after a modification of step 3) in the secondary of step 4)
In modified sizing agent, it is ultrasonically treated more than 48 hours under normal temperature, obtains the sample after twice-modified processing, the sample is placed on drum
Dried in wind drying box, obtain modified carbon fiber sample；
6) the modified carbon fiber sample that step 5) obtains is imported into resin transfer molding technique by vacuum, changed
Property carbon fiber reinforced epoxy resin-based composite.
A kind of product, the product are made using above-mentioned modified carbon fiber reinforced epoxy based composites.
Relative to prior art, beneficial effect possessed by the present invention：
The marked improvement of preparation method of the present invention is：Carbon fiber surface is modified using double sizing agent hybrid modifications,
Analysis is carried out with material analysis method to find, it is twice-modified to handle the microscopic appearance for improving carbon fiber surface.Specifically, its boundary
Face cutting performance is effectively improved, and interface binding power improves 24%；After being prepared into composite, its tensile property obtains
Improve, the ultimate tensile strength of composite improves 29%；During stretching experiment, due between carbon fiber and resin
Adhesion increase so that in composite, carbon fiber is extracted obvious less, and the tension failure of composite board is how fine with carbon
Based on the fracture for tieing up silk itself, the mechanical property of carbon fiber reinforced epoxy resin-based composite is significantly improved.
The substantive distinguishing features that preparation method of the present invention protrudes are：
1) appropriate amino multi-walled carbon nanotube, which is dissolved in the solution containing silane coupler, is made preimpregnation sizing agent, passes through
Sizing agent infiltration, the method for high temperature sintering are to carbon fiber surface modification；
2) OA-POSS and SiO is utilized2Twice-modified sizing agent after mixing, modified carbon fiber surface is infiltrated once,
It is dried to obtain the carbon fiber with final modified layer.Above-mentioned final modified layer can be boundary layer, and this boundary layer is different from other
The multiple solutions characteristic that multicomponent is modified, its interface is only OA-POSS one layer of cage structure, because inside cage structure
Space it is bigger so that the dendritic morphology and SiO of CNT2Powdered granule be entrained in the inside, ultimately form carbon fibre
An interfacial layer between dimension and epoxy resin, less boundary layer preferably add the combination between carbon fiber and resin
Power, so that composite material exhibits go out preferable interface feature.Described interface feature has interface thing phase constituent, material modified
Composition and purity, the position of modification, interfacial layer thickness, the peel strength etc. at interface.
3) carbon cloth is subjected to laying, resin transfer molding technique (Vacuum Assisted is imported using vacuum
Resin Transfer Molding, english abbreviation VARTM) it is molded, to composite wood under 0.1MPa atmospheric pressure
It is prepared by material, so as to be made dense uniform, flatness it is good carbon fiber reinforced epoxy resin-based composite plate is made
Material.
4) material that the surface second after pre-treatment of carbon fiber is modified is respectively amino multi-walled carbon nanotube and eight ammonia third
Polyhedral oligomeric silsesquioxane mixes SiO2.The modification technology taken of the present invention can ensure the performance of carbon fiber with
On the premise of slight, the combination between carbon fiber and resin is further improved.Pass through 0.5-2.0% in carbon fiber surface
Amino multi-walled carbon nanotube is modified, and can increase carbon fiber surface activity key, such as amino and carboxyl etc., and add carbon fiber
Surface roughness, so as to enhance the combination between carbon fiber and resin；When content of carbon nanotubes is less than 0.5%, carbon
The content of carbon nanotubes of fiber surface grafting is very few, it is impossible to the preferably roughness of increase fiber surface, when containing for CNT
When amount is higher than 1.0%, it may appear that slight agglomeration, after further increasing to 2.0%, the carbon nanometer of carbon fiber surface
Pipe too high levels, easily cause the reunion of CNT so that CNT becomes the fragile phase at interface, reduces carbon fibre on the contrary
Combination between dimension and resin；It is preferred that the content of amino multi-walled carbon nanotube is 0.5~1.0%.For being once modified starching
The problem of CNT and epoxy-resin systems are inconsistent in agent, for the method for twice-modified sizing agent processing, OA- is used
POSS, this high polymer are easier to be combined with epoxy resin, and high polymer belongs to SiO2It is thing, if appropriate addition SiO2, make
It is distributed in inside cage type high polymer and forms good mix with CNT so that interaction between modifying interface compared with
By force, the combination of interface and epoxy resin is more beneficial for, significantly increases the adhesion between carbon fiber surface and epoxy；This
Outside, prepare composite and resin transfer molding technique VARTM is imported using vacuum, its interface shearing is tested real with stretching
Analysis is tested, its mechanical property has obtained a certain degree of raising, and wherein cutting performance improves 24%, and tensile property improves
29%.
Brief description of the drawings
Fig. 1 is the schematic diagram of the VARTM equipment used in the present invention.
Fig. 2 is the carbon fiber surface being modified respectively according to comparative example 1, comparative example 2, embodiment 1, embodiment 2 and embodiment 3
ESEM map analysis.
Fig. 3 is the carbon fiber surface being modified respectively according to comparative example 1, comparative example 2, embodiment 1, embodiment 2 and embodiment 3
Interface shear strength comparison diagram.
Fig. 4 is the composite panel prepared respectively according to comparative example 1, comparative example 2, embodiment 1, embodiment 2 and embodiment 3
The stress-strain curve of the tensile strength of material.
Embodiment
The present invention is described in further detail below in conjunction with drawings and examples.It should be appreciated that tool described herein
Body embodiment only to explain the present invention, is not intended to limit the present invention.
Preparation method (the referred to as preparation side of double sizing agent modified carbon fiber reinforced epoxy based composites of the invention
Method), be the step of this method：
1) carbon nano-tube modification solution is prepared：Silane coupler is dissolved in ethanol solution, stirring obtains silane coupled
Agent colloidal sol；Then silane coupler colloidal sol, amino multi-walled carbon nanotube are added separately in dispersant, in rotating speed 800-
Carbon nano-tube modification solution, as CNT (amino multi-walled carbon nanotube) sizing agent or one are uniformly mixing to obtain under 2000r/min
Secondary modified sizing agent；The mass percent of each material is in the carbon nano-tube modification solution：0.1-0.8% silane couplers are molten
Glue, 0.5-2.0% amino multi-walled carbon nanotube, 97.2%-99.4% dispersants；The dispersant be acetone, alcoholic solution or
Person can play other reagents of peptizaiton；
2) carbon fiber surface pre-processes：Carbon cloth is immersed in cleaner and carries out surface clean, after then cleaning
Carbon cloth be dried and high temperature oxidation process, the high-temperature oxydation temperature is 300-600 DEG C, and the high-temperature oxydation time is
10-60min；Carbon cloth after oxidation processes is cooled to normal temperature, is placed in sample bag；
The cleaner is the mixed solution that acetone, alcoholic solution or both are mixed with arbitrary proportion；
3) modification of carbon fiber：The pretreated carbon cloth of step 2) is immersed in carbon nano-tube modification solution
In, carbon cloth is taken out after ultrasonic vibration 50-90s, and be dried at normal temperatures；Then carbon cloth is placed on full of argon
In the tube furnace of gas, 2-5h is sintered at 600-900 DEG C, after being cooled to normal temperature, argon gas is closed, takes out sample；
4) twice-modified sizing agent is prepared：The SiO that particle diameter is 20nm-1 μm is prepared by raw material of tetraethyl orthosilicate2Powder；
Then by octa-aminopropyl polyhedral oligomeric silsesquioxane (OA-POSS) and SiO2Powder is dissolved in distilled water, and octa-aminopropyl is more
Face body oligomeric silsesquioxane (OA-POSS), SiO2The mass percent of powder and distilled water is 0.5%：0.5-1.0%：
98.5-99.0%, under conditions of bath temperature is 60-100 DEG C, rotating speed is 500-1500r/min, stop after stirring 0.5-2h
Heating, standing arrive room temperature, obtain required twice-modified sizing agent；
5) the twice-modified processing of carbon fiber：It will be infiltrated through the sample after a modification of step 3) in the secondary of step 4)
In modified sizing agent, it is ultrasonically treated more than 48 hours under normal temperature, obtains the sample after twice-modified processing, the sample is placed on drum
In wind drying box, air drying 0.5-3h, modified carbon fiber sample is obtained；
6) the modified carbon fiber sample that step 5) obtains is imported into resin transfer molding (VARTM) work by vacuum
Skill, obtain modified carbon fiber reinforced epoxy based composites.
Further, silane coupler used during carbon nano-tube modification solution is prepared as coupling agent KH550, it is used scattered
Agent is that proportioning is (4~8):(2~4):Oleic acid, octadecyl alcolol, the ethanol solution of neopelex of (1~2).
Further, SiO is prepared2Powder comprises the concrete steps that：Tetraethyl orthosilicate is dissolved in ethanol solution, in 40-70
It is stirred continuously at a temperature of DEG C and under 800-1500r/min rotating speed, and ammoniacal liquor, which is added dropwise, is maintained at the pH value of solution
The mass percent of 9.5-11, tetraethyl orthosilicate and ethanol solution is 40%-70%；When stirring transparent gluey to solution,
Stop heating and stirring, it is in solid-like that obtained clear gum thing is placed in into drying in 80-120 DEG C of drying box, is ground into phase
The white particle of particle diameter is answered, that is, obtains SiO2Powder.
Further, it is material modified to act on carbon fiber surface, boundary layer, the thickness of boundary layer are formed between epoxy resin
Spend for 0.8-12 μm.
Bisphenol A type epoxy resin can be at least one of E51, E44, E42, E54, E20, E06, E35；Phenolic aldehyde amine is consolidated
Agent is any one matched with corresponding resin.
The composite board thickness is 1-2mm, and hybrid modification material is the high-molecular compound of chemical bonding；It is described
High-molecular compound, it is characterised in that：Described chemical bonding mode include amino carboxylic-bond, electron cloud π electrostatic interactions,
Carbon key such as is combined at a variety of combinations with the sp hydridization of half siloxanes.
The present invention also protects a kind of carbon cloth obtained after above-mentioned twice-modified processing.
The present invention also protects a kind of modified carbon fiber reinforced epoxy base composite wood obtained by above-mentioned preparation method
Flitch material.
The thickness of the composite board is 1.0-2.5mm, and 15%-30% is improved before tensile strength is more unmodified.
The carbon cloth is T300 or T800, T1200 etc., and the epoxy resin is epoxy resin E51 or others
Bisphenol A type epoxy resin, the curing agent used in vacuum assisted resin infusion can be T31 or 651 etc..
Equipment (referring to Fig. 1) in the present invention used in vacuum assisted resin infusion includes Teflon mould 2, scribbles the demoulding
The release cloth 8 of agent, flow-guiding screen 7, mozzle 6, vacuum tube 1, vacuum bag 5, resin trap etc..The releasing agent be paraffin or
Other chemical reagent of demoulding effect can be played.The mould is that polytetrafluoroethylmaterial material machining is made.By step 5)
Obtained carbon cloth sample is placed on Teflon mould 2, and carries out laying, and ply stacking-sequence is carbon cloth from the bottom up
4th, release cloth 8, flow-guiding screen 7, vacuum bag 5；Vacuum bag is fixed on Teflon mould by vacuum glue 3, and 1,9 point of vacuum tube
It is not fixed on the mould of carbon cloth both sides, and one end connection mozzle 6 of vacuum tube.Specific embodiment is：Use clip
Clamp vacuum tube 1, vavuum pump connection vacuum tube 9, vacuum tube 9 is vacuumized, when to be extracted into vacuum pressure be -0.1MPa, use clip
Vacuum tube 9 is clamped, closes vavuum pump, the pressurize 1h under -0.1MPa, registration keeps constant, then again prepares the insertion of vacuum tube 1
Evacuated epoxy resin solution in；Remove the clip of vacuum tube 1 and vacuum tube 9, open vavuum pump, epoxy resin enters
Enter into vacuum space, thus epoxy resin is infiltrated on the surface of carbon cloth, solidification 6h or so, disassembles the technique, and then
The good carbon fiber sheet of surface quality is obtained, then the carbon fiber sheet to obtaining is cut, and carry out stretching experiment test.
Modified carbon fiber reinforced epoxy based composites of the present invention are through correlated performance experiment test, peel strength
0.7-10N, interface shear strength 75.89-80.48MPa；The monofilament tensile strength of modified carbon fiber sample is 297-
592MPa。
Embodiment 1
Amino multi-walled carbon nanotube (CNTs) used wins the limited public affairs of space high-tech new material technology for Beijing in the present embodiment
Department's purchase, purity 98%-99.999%；Octa-aminopropyl polyhedral oligomeric silsesquioxane (OA-POSS) is that Hebei industry is big
Learn chemical engineering institute to provide, purity 97%-99.988%；Tetraethyl orthosilicate (TEOS) concentration is more than 95%, ethanol (C2H5OH)
Concentration is 70%-90%, ammoniacal liquor (NH3OH) concentration is 70%-80%, and above Essential Chemistry material is the pure thing of chemical analysis
Matter.Carbon cloth is T300.
The step of preparation method of the double sizing agent modified carbon fiber reinforced epoxy based composites of the present embodiment is：
1) carbon nano-tube modification solution is prepared：Silane coupler is dissolved in ethanol solution, is 1000r/min in rotating speed
Lower stirring obtains silane coupler colloidal sol；Then silane coupler colloidal sol, amino multi-walled carbon nanotube are added separately to disperse
In agent, carbon nano-tube modification solution is uniformly mixing to obtain under rotating speed 1500r/min, i.e., is once modified sizing agent；The carbon is received
The mass percent of each material is in mitron modified solution：0.5% silane coupler colloidal sol, 0.8% amino multi-walled carbon nanotube,
98.7% dispersant；The dispersant is acetone；
2) carbon fiber surface pre-processes：Carbon cloth is immersed in cleaner and carries out surface clean, after then cleaning
Carbon cloth be dried and high temperature oxidation process, carbon cloth is placed in blast drier, temperature setting is 80 DEG C, is done
Dry 1h, carbon cloth is placed in Muffle furnace, and high-temperature oxydation 30min, is cooled to normal temperature under the conditions of 400 DEG C, is placed in sample bag
In.The cleaner is acetone；
3) modification of carbon fiber：The pretreated carbon cloth of step 2) is immersed in carbon nano-tube modification solution
In, carbon cloth is taken out after ultrasonic vibration 60s, and dry 2h at normal temperatures；Then carbon cloth is placed on full of argon gas
In tube furnace, 5h is sintered at 900 DEG C, after being cooled to normal temperature, argon gas is closed, takes out sample；
4) twice-modified sizing agent is prepared：Tetraethyl orthosilicate is dissolved in ethanol solution, at a temperature of 60 DEG C and
It is stirred continuously under 1500r/min rotating speed, and ammoniacal liquor, which is added dropwise, makes the pH value of solution be maintained at 10, tetraethyl orthosilicate and ethanol
The mass percent of solution is 70%；When stirring transparent gluey to solution, stop heating and stirring, the transparent adhesive tape that will be obtained
It is in solid-like that shape thing, which is placed in drying in 100 DEG C of drying box, is ground into the white particle of corresponding particle diameter, that is, obtaining particle diameter is
100nm SiO2Powder；Then by octa-aminopropyl polyhedral oligomeric silsesquioxane (OA-POSS) and SiO2Powder is dissolved in distillation
In water, octa-aminopropyl polyhedral oligomeric silsesquioxane (OA-POSS), SiO2The mass percent of powder and distilled water is
0.5%：1.0%：98.5%, under conditions of bath temperature is 80 DEG C, rotating speed is 1500r/min, stop heating after stirring 1h,
Room temperature is stood, obtains required twice-modified sizing agent；
5) the twice-modified processing of carbon fiber：It will be infiltrated through the sample after a modification of step 3) in the secondary of step 4)
In modified sizing agent, 72h is ultrasonically treated under normal temperature, obtains the sample after twice-modified processing, the sample is placed on forced air drying
In case, air drying 1h, modified carbon fiber sample is obtained；
6) the modified carbon fiber sample that step 5) obtains is imported into resin transfer molding (VARTM) work by vacuum
Skill, obtain modified carbon fiber reinforced epoxy based composites.
Vacuum import resin transfer molding detailed process be：5) the carbon cloth sample obtained in is placed on polytetrafluoroethyl-ne
On alkene mould, and laying is carried out, ply stacking-sequence is from the bottom up carbon cloth 4, release cloth 8, flow-guiding screen 7, vacuum bag 5；Vacuum
Bag is fixed on Teflon mould by vacuum glue 3, and vacuum tube 1,9 is separately fixed on the mould of carbon cloth both sides,
And one end connection mozzle 6 of vacuum tube.Specific embodiment is：Vacuum tube 1 is clamped with clip, vavuum pump connects vacuum tube 9,
Vacuum tube 9 is vacuumized, when to be extracted into vacuum pressure be -0.1MPa, vacuum tube 9 clamped with clip, closes vavuum pump, -
Pressurize 1h under 0.1MPa, registration keep constant, then again inserted vacuum tube 1 in the epoxy resin solution vacuumized prepared；
Remove the clip of vacuum tube 1 and vacuum tube 9, open vavuum pump, epoxy resin is entered in vacuum space, thus by epoxy resin
Infiltrate on the surface of carbon cloth, solidification 6h or so, disassemble the technique, and then obtain the good carbon fiber sheet of surface quality,
Obtained carbon fiber sheet is cut again, and carries out stretching experiment test.
Embodiment 2
The present embodiment prepares each steps of modified carbon fiber reinforced epoxy based composites with embodiment 1, difference
The mass percent for being in each material in carbon nano-tube modification solution described in the present embodiment is：0.5% silane coupler is molten
Glue, 1.0% amino multi-walled carbon nanotube, 98.5% dispersant.
Embodiment 3
With embodiment 1, difference exists each step of the present embodiment modified carbon fiber reinforced epoxy based composites
The mass percent of each material is in carbon nano-tube modification solution described in the present embodiment：0.5% silane coupler colloidal sol,
2.0% amino multi-walled carbon nanotube, 97.5% dispersant.
Comparative example 1
This comparative example prepares carbon fiber epoxy based composites, comprises the concrete steps that：
1) carbon fiber surface pre-processes：Carbon cloth is immersed in cleaner, cleaner is acetone, soaks 30min, will
Carbon cloth is placed in blast drier, and temperature setting is 80 DEG C, dries 1h, dried carbon cloth is placed in into Muffle furnace
In, high-temperature oxydation 30min, is cooled to normal temperature under the conditions of 400 DEG C, is placed in sample bag.
2) pretreated carbon cloth is imported into resin transfer molding (VARTM) technique by vacuum, obtains carbon
Fibrous epoxy resin based composites.
Comparative example 2
This comparative example prepares the carbon fiber epoxy based composites being only modified with sizing agent is once modified, according to implementation
After the progress carbon nano-tube modification solution preparation of the step of example 1, carbon fiber surface pretreatment and modification of carbon fiber directly
Carry out vacuum and import resin transfer molding (VARTM) technique, obtain the carbon fiber ring being only modified with sizing agent is once modified
Epoxy resin-based composite.
Here is the experimental analysis of comparative example 1, comparative example 2, embodiment 1, embodiment 2 and embodiment 3.
It is illustrated in figure 2 and prepares test according to the method for comparative example 1, comparative example 2, embodiment 1, embodiment 2 and embodiment 3
The scanning electron microscope (SEM) photograph of carbon fiber wire, wherein comparative example 1 are unmodified carbon fiber wire, and its surface is clear by ethanol and acetone
After washing, it can be seen that the texture of carbon fiber surface after after cleaning；And comparative example 2 is to be handled by carbon nano-tube modification solution,
Its surface is clearly present the projection of some CNT aggregations.Comparative example 1 and comparative example 2 and embodiment 1 are contrasted, it can be seen that pass through
The carbon fiber surface of embodiment 1 modified twice there's almost no without significant gully, the dendritic projection of excessive carbon fiber,
This explanation, appropriate CNT are interspersed in OA-POSS cage structure, the CNT and OA-POSS/SiO of moderate contents2Infiltrate twice
More preferable boundary layer can be obtained.The CNT modified methods of different quality containing will also result in technique to the surface topography of carbon fiber
Different influences, embodiment 1, embodiment 2, embodiment 3 are respectively the modification under various concentrations in Fig. 2, it is seen that different concentration
Certain influence is will also result in carbon fiber surface modification, is made discovery from observation, when the mass fraction of CNT is where appropriate, such as
Shown in embodiment 1, CNT is more uniformly passed through in OA-POSS cage structure, causes boundary layer to be distributed in the surface of carbon fiber
On.When embodiment 2 is that content is smaller, different gloss is presented in carbon fiber surface, because part OA-POSS injection CNT,
And part does not have injection, cause the distribution of color of carbon fiber surface not uniform enough, surface smoothness is also poor.And in embodiment 3,
The more contents of CNT, the aggregation extent of injection is larger, CNT clustering phenomenas occurs, also have impact on the combination energy between interface and resin
Power.But although to can be seen that its surface raised uneven by the CNT after embodiment 2 and embodiment 3 are handled, it is
Carbon fiber has been enveloped completely in itself so that there are OA-POSS (SiO between carbon fiber and resin2) exist with CNT, cause-NH2-
With being bonded for-COOH, the epoxide group between-SiO- and resin connects, thus the interface of embodiment 2 and embodiment 3 is obvious
It is better than comparative example 1 and comparative example 2.
It is illustrated in figure 3 the carbon fiber wire prepared according to comparative example 1, comparative example 2, embodiment 1, embodiment 2 and embodiment 3
Interface shear strength comparison diagram, contrast understand, embodiment 1, embodiment 3, the interface shear strength of embodiment 3 have obtained one
Determine the improvement of degree, the shear strength compared to untreated comparative example 1 and the embodiment of comparative example 2 is significantly improved, real
The shear strength for applying example 1 is 80.47MPa, compared to the 64.86MPa of comparative example 1, the 69.88MPa of comparative example 2, is respectively increased
24.07%, 15.15%；Different carbon nanotube mass fractions will also result in different to the cutting performance of composite
Influence, when the mass fraction of CNT is 0.5%1.0%, cutting performance is most strong, is 80.47MPa.
It is illustrated in figure 4 the carbon fiber board prepared according to comparative example 1, comparative example 2, embodiment 1, embodiment 2 and embodiment 3
The tensile stress-strain curve comparison diagram of material：Contrast understand embodiment 1, embodiment 2, embodiment 3 modulus of elasticity there occurs
Change, the tensile property of especially embodiment 1 generates very big influence, its modulus of elasticity has been reached 5000MPa, and carbon is fine
The performance of dimension composite is improved and optimized.For embodiment 2 with embodiment 3 relative to comparative example 1 and comparative example 2, it should
Force intensity change is not very greatly, because very few or too high amount CNT can make it that boundary layer is uneven, but because necessarily
- the NH2- and-COOH of degree are bonded, and-SiO- is connected with resin epoxide group and the presence meeting of OA-POSS cage structure
So that its coefficient of strain increases, by the 0.065% of comparative example 1 and comparative example 2,0.068% becomes embodiment 2 and embodiment 3
0.074%, 0.080%, that is, cause embodiment 1, the plasticity of embodiment 2 and embodiment 3 to improve.
In summary, to interface shearing performance, the tensile strength of carbon fiber by the way of double sizing agents of the invention are modified
Exert a certain influence, the mechanical property of modified carbon fiber wire has obtained relatively obvious improvement.In addition, for changing
For the amino multi-walled carbon nanotube of property, appropriate concentration should be selected, excessive concentration or it is too low can be to fibre reinforced tree
The intensity of resin-based composite has adverse effect on.
Described above is only the preferred embodiment of the present invention, it is noted that for the common skill of the art
For art personnel, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications
Also it should be regarded as protection scope of the present invention.
Claims (7)
1. it is a kind of preparation method of double sizing agent modified carbon fiber reinforced epoxy based composites, the step of this method：
1）Prepare carbon nano-tube modification solution：Silane coupler is dissolved in ethanol solution, it is molten that stirring obtains silane coupler
Glue；Then silane coupler colloidal sol, amino multi-walled carbon nanotube are added separately in dispersant, in rotating speed 800-2000 r/
Carbon nano-tube modification solution is uniformly mixing to obtain under min；The mass percent of each material is in the carbon nano-tube modification solution：
0.1-0.8% silane couplers colloidal sol, 0.5-2.0% amino multi-walled carbon nanotube, 97.2%-99.4% dispersants；
2）Carbon fiber surface pre-processes：Carbon cloth is immersed in cleaner and carries out surface clean, then by the carbon after cleaning
Fiber cloth is dried and high temperature oxidation process, and the high-temperature oxydation temperature is 300-600 DEG C, and the high-temperature oxydation time is 10-60
min；Carbon cloth after oxidation processes is cooled to normal temperature, is placed in sample bag；
3）Modification of carbon fiber：By step 2）Pretreated carbon cloth is immersed in carbon nano-tube modification solution,
Carbon cloth is taken out after ultrasonic vibration 50-90 s, and is dried at normal temperatures；Then carbon cloth is placed on full of argon gas
Tube furnace in, at 600-900 DEG C sinter 2-5 h, after being cooled to normal temperature, close argon gas, take out sample；
4）Prepare twice-modified sizing agent：The SiO that particle diameter is 20nm-1 μm is prepared by raw material of tetraethyl orthosilicate2Powder；Then will
Octa-aminopropyl polyhedral oligomeric silsesquioxane（OA-POSS）With SiO2Powder is dissolved in distilled water, and octa-aminopropyl polyhedron is low
Polysilsesquioxane（OA-POSS）、SiO2The mass percent of powder and distilled water is 0.5%：0.5-1.0%：98.5-99.0%；
Under conditions of bath temperature is 60-100 DEG C, rotating speed is 500-1500 r/min, stirring stops heating to after being thoroughly mixed,
Room temperature is stood, obtains required twice-modified sizing agent；
5）The twice-modified processing of carbon fiber：Will be through step 3）Sample after modification is infiltrated in step 4）It is twice-modified
In sizing agent, it is ultrasonically treated more than 48 hours under normal temperature, obtains the sample after twice-modified processing, the sample is placed on into air blast does
Dried in dry case, obtain modified carbon fiber sample；
6）By step 5）Obtained modified carbon fiber sample imports resin transfer molding technique by vacuum, obtains carbon modified
Fiber reinforced epoxy resin based composites.
2. the preparation method of double sizing agent modified carbon fiber reinforced epoxy based composites according to claim 1,
It is characterized in that the dispersant is acetone or alcoholic solution or proportioning is (4 ~ 8):(2~4):The oleic acid of (1 ~ 2), octadecyl alcolol, ten
The ethanol solution of dialkyl benzene sulfonic acids sodium.
3. the preparation method of double sizing agent modified carbon fiber reinforced epoxy based composites according to claim 1,
Characterized in that, prepare SiO2Powder comprises the concrete steps that：Tetraethyl orthosilicate is dissolved in ethanol solution, in 40-70 DEG C of temperature
It is stirred continuously under degree and under 800-1500r/min rotating speed, and ammoniacal liquor, which is added dropwise, makes the pH value of solution be maintained at 9.5-11, just
The mass percent of silester and ethanol solution is 40%-70%；When stirring transparent gluey to solution, stop heating and stir
Mix, it is in solid-like that obtained clear gum thing is placed in into drying in 80-120 DEG C of drying box, is ground into the white of corresponding particle diameter
Particle, that is, obtain SiO2Powder.
4. the preparation method of double sizing agent modified carbon fiber reinforced epoxy based composites according to claim 1,
It is characterized in that boundary layer can be formed between the carbon fiber and epoxy resin of modified carbon fiber reinforced epoxy based composites,
Interfacial layer thickness is 0.8-12 μm.
5. the preparation method of double sizing agent modified carbon fiber reinforced epoxy based composites according to claim 1,
Characterized in that, silane coupler is coupling agent KH550；The epoxy resin is E51, E44, E42, E54, E20, E06, E35
At least one of.
6. the preparation method of double sizing agent modified carbon fiber reinforced epoxy based composites according to claim 1,
It is characterized in that the detailed process that vacuum imports resin transfer molding technique is：Vacuum tube is clamped with clip（1）, vavuum pump
Vacuum tube is connected, to vacuum tube（9）Vacuumize, when to be extracted into vacuum pressure be -0.1MPa, vacuum tube is clamped with clip（9）, close
Vavuum pump, the pressurize 1h under -0.1MPa, registration keeps constant, then again by vacuum tube（1）Insertion prepares evacuated
In epoxy resin solution；Remove vacuum tube（1）With vacuum tube（9）Clip, open vavuum pump, epoxy resin enter vacuum sky
In, thus epoxy resin is infiltrated on the surface of carbon cloth, solidification 6h or so, disassembles the technique, and then obtain surface matter
Good carbon fiber sheet is measured, then the carbon fiber sheet to obtaining is cut, and carry out stretching experiment test.
7. a kind of product, it is characterised in that the product usage right requires any described modified carbon fiber reinforced epoxy trees of 1-6
Resin-based composite is made.
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