CN105968718A - Preparation method of carbon fiber/graphene/epoxy resin prepreg and carbon fiber composite material - Google Patents
Preparation method of carbon fiber/graphene/epoxy resin prepreg and carbon fiber composite material Download PDFInfo
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- CN105968718A CN105968718A CN201610339876.8A CN201610339876A CN105968718A CN 105968718 A CN105968718 A CN 105968718A CN 201610339876 A CN201610339876 A CN 201610339876A CN 105968718 A CN105968718 A CN 105968718A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
Abstract
The invention provides preparation methods of a carbon fiber/graphene/epoxy resin prepreg and a carbon fiber composite material and belongs to the field of preparation of carbon fiber composite materials. By carrying out surface modification on graphene prepared by adopting an improved Hummers method and grafting -NH2 on the surface or the edge of the graphene, the dispersity of the graphene in a resin substrate is improved; and meanwhile, the interface bonding force between a micron-grade carbon fiber and an epoxy resin substrate can be effectively increased and gap defects are reduced, so that the mechanical properties of an epoxy resin based composite material are improved. When the adding amount of the carbon fiber/graphene/epoxy resin prepreg and carbon fiber composite material provided by the invention is 0.5wt%, the mechanical properties are optimal; the bending strength reaches 1525.4MPa and the interlayer shearing strength reaches 91.14MPa; and compared with a carbon fiber enhanced epoxy resin composite material, the bending strength and the interlayer shearing strength are improved by 15.41% and 14.14% respectively. The preparation method has the characteristics of simple process, small solvent toxin, applicability of industrial production and the like.
Description
Technical field
The present invention relates to the preparation method of a kind of composite, a kind of unidirectional carbon/Graphene/
Epoxy prepreg and the preparation method of carbon fibre composite.
Background technology
Carbon fiber-reinforced resin composite materials (CFRP) have excellence specific strength, specific stiffness, corrosion-resistant,
The performances such as endurance and high use temperature, are widely used in Aero-Space, sports equipment and defence and military industry.
What in carbon fiber-reinforced resin composite materials, matrix application was most is epoxy resin, and epoxy resin has good sticking
Knot property, thermostability, resistance to corrosive chemicals, high intensity and the series of advantages such as easy to process, but material
Fracture elongation is relatively low, fragility is relatively big, and its solidfied material is the most poor with the associativity of fiber, had a strong impact on its
Application in Aero-Space.
Prepreg is fiber or its fabric drying of the impregnating resin system for manufacturing polymer matrix composites
Or the intermediate of pre-polymerization, it is the main intermediate materials manufacturing composite material structural member.The raw material of prepreg includes
Reinforcement and matrix, main auxiliary material is release paper and embossing polyethylene film etc., the increasing that prepreg is conventional
Strong body is mainly carbon fiber, aramid fiber, glass fibre and their fabric, and prepreg resin matrix includes heat
Thermosetting resin and the big class of thermoplastic resin two.The actually used major part of carbon fiber is to pass through carbon fibre initial rinse at present
The mode of material realizes, and in order to give full play to the superhigh intensity performance of carbon fiber, is substantially all and needs to make carbon fiber
One-tenth only has radial distribution, does not has the prepreg of the unidirectional fibre of Zonal propagations.The good and bad directly shadow of prepreg quality
Ring the overall performance of composite, by optimization processing technology and add different types of reinforcement and can promote pre-
The performance of leaching material.
In addition to carbon fiber itself is carried out surface modification, multi-scale enhancement is a kind of more common means, i.e.
One or more other nano structural materials are added, such as aerosil, nanometer in carbon fibre composite
Clay, CNT, Graphene etc..Graphene is by sp2It is cellular that hydbridized carbon atoms piles up having of formation
The monolayer carbon material of lattice structure, has the characteristics such as the high conductivity of excellence, high intensity, ultra-thin due to it,
Become the most promising reinforcing material in polymer composites, be combined especially for toughness reinforcing reinforced epoxy
Material.Rubber adds epoxy resin can make system viscosity increase, and improves the shock resistance of composite prepared by it
Property, reach toughness reinforcing effect.
In traditional composite, Graphene exists in polymeric matrix as the reinforcement of a kind of composite
The poor shortcoming of poor and with polymeric matrix the interface cohesion effect of dispersibility, and carbon fiber is as reinforcement
Its surface-active functional group is few, and bad adhesion and have defect in various degree between matrix resin wellability, thus
Cause Graphene or carbon fiber enhancement resin base composite material interfacial bond strength is low, bad mechanical property, it addition,
The epoxy resin composite material of traditional single dimension reinforcement sometimes can carry while some performance improves
The decline of other performances dynamic.
Summary of the invention
The invention provides a kind of carbon fiber/graphite alkene/epoxy prepreg and the system of carbon fibre composite thereof
Preparation Method, can effectively solve Graphene and carbon fiber applied defect in the composite.By graphite oxide-
Thermal expansion reduction-ultrasonic Graphene peeling off preparation often contains some hydroxyl functional bases at its basal plane and edge
Group, and these groups can be as carrying out, with silane coupler, the avtive spot that reacts, and then at graphenic surface
Grafted amino group, the Graphene modified by ammonia can significantly improve the interface between Graphene and epoxy resin-base
Adhesive capacity, improves Graphene dispersibility in resin matrix, and Graphene and carbon fiber are all material with carbon elements, and two
Person has the highest compatibility, nano level Graphene and micron order carbon fiber is combined, can be obviously improved tree
The performance of resin-based composite.
For achieving the above object, the present invention is by the following technical solutions:
The preparation method of a kind of carbon fiber/graphite alkene/epoxy prepreg, comprises the following steps successively:
(1) preparation of Graphene
Preferably: weigh NaNO3Solid is dissolved in the concentrated sulphuric acid of 98%, is placed in ice-water bath by mixed liquor simultaneously
Stirring makes NaNO3Solid fully dissolves；Weigh graphite to join in above-mentioned mixed liquor, stir；With
After, it is slowly added to excess potassium permanganate and aoxidizes, adition process controls reaction temperature and is less than 20 DEG C,
Stir, temperature is transferred to 30-40 DEG C and continues stirring reaction；Then in mixed liquor, deionized water is added dilute
Release and drip H2O2, make solution become glassy yellow；Filter, with the hydrochloric acid of mass concentration 5% while filtering
Solution washs；The filter cake deionized water dilution obtained after filtering, then carry out ultrasonic and centrifugal treating；From
The supernatant obtained after the heart adds hydrochloric acid solution, is sufficiently stirred for rear recentrifuge；Under obtaining after being centrifuged
Layer viscous solid is dried, and obtains graphite oxide sample；Take gained graphite oxide, quickly put into and be preheated to
The Muffle furnace of 1050 DEG C keep 30s obtain expanded graphite alkene；Take expanded graphite alkene and add in dehydrated alcohol,
Ultrasonic stripping is not higher than 15h, and vacuum drying obtains Graphene；
(2) by Graphene and N, N'-Dicyclohexylcarbodiimide (DCC) is dispersed in amino silicane coupling agent solution
In, by ultrasonic for mixed liquor 1～3 hour, the homogeneous mixture of black is heated to 60～80 DEG C, stirs 12～20
Hour, it is then centrifuged for separating and cleaning with deionized water, gains is placed in vacuum drying oven and is dried, obtain ammonia
Modified graphene；
(3) the ammonia modified graphene of gained in step (2) is joined epoxy resin, polyurethane-modified liquid
In rubber and curing agent composition system, mechanical agitation ultrasonic reaction 4～8h, add accelerator (DMP-30),
And continue ultrasonic reaction 1～2h；Then, (true as at 50 DEG C of de-bubbled in vacuum drying oven is placed reaction liquid into
De-bubbled 1～2h in empty baking oven)；Obtain Graphene/epoxy resin serosity；
(4) Graphene obtained above/epoxy resin serosity is poured in steeping vat, and place in steeping vat
Having supersonic generator, then immerse in steeping vat by carbon fibre tow, the tow after impregnation is gone by spreading roller
Except unnecessary resin adhesive liquid, the tow after impregnation is arranged silk by the way of row's silk machine uses winding, is repeatedly twined
Around, preferably amount to and be repeatedly wound around 2～4 layers, under the conditions of 100～120 DEG C, be dried 1～4h, obtain unidirectional carbon fiber
Dimension/Graphene/epoxy prepreg.
Prepreg is prepared laminate by flat-bed press press curing, solidifies after carrying out in an oven, cold
But to room temperature, carbon fibre composite is obtained.
Preferably, described in above-mentioned steps (1), graphite is natural flake graphite, and Graphene is single or multiple lift
Graphene.
Preferably, the amino silicane coupling agent described in above-mentioned steps (2) is 3-aminopropyl triethoxysilane,
Graphene dispersion concentration in 3-aminopropyl triethoxysilane is 0.5～2mg/ml.
Preferably, the Graphene described in above-mentioned steps (2) and dehydrant N, N'-Dicyclohexylcarbodiimide
(DCC) mass ratio is 10:3～5.
Preferably, the composition epoxy resin component described in above-mentioned steps (3) includes epoxy resin, poly-ammonia
Ester modified liquid rubber and firming agent, firming agent is MDA or methyl tetrahydro phthalic anhydride, accelerator
For 2,4,6-tri-(dimethylamino methyl) phenol.
Preferably, each constituent mass ratio epoxy resin in the composition system described in above-mentioned steps (3):
Polyurethane-modified liquid rubber: firming agent MDA is 100:5～15:25～40, or epoxy resin:
Polyurethane-modified liquid rubber: firming agent methyl tetrahydro phthalic anhydride is 100:5～15:60～70, the epoxy of every 100 parts
The amount adding accelerator in resin is 1ml.
Preferably, the quality of the ammonia modified graphene described in above-mentioned steps (3) is epoxy resin quality
0.05～1%.
Above-mentioned epoxy resin is preferably epoxy resin E51.
Preferably, described composite solidification process is to solidify at 90 DEG C 1～2 hour, then solid at 130 DEG C
Change 2～4 hours, solidify 2～4 hours at last 150 DEG C.
A kind of carbon fiber/graphite alkene/epoxy prepreg is unidirectional pre-immersion material, by logical after carbon fibre tow impregnation
The row's of mistake silk machine is wound around row's silk and obtains.
Compared with prior art, the technical scheme that the present invention provides has a following excellent effect:
1, the technical scheme that the present invention provides have employed the ammonia modified graphene of nano-scale dimension and improves Graphene
It is prone to the drawback reunited, by the chemical bonds between amino and resin matrix, improves Graphene at resin
Dispersibility in matrix, and and matrix between have preferable interfacial interaction.At carbon fiber/graphite alkene/epoxy
In resin composite materials, appropriate ammonia modified graphene can not only play overseas Chinese federation well between fiber and matrix
Effect, decreases the generation of void defects, simultaneously its well dispersibility contribute to uniformly transferring of plus load.
2, resin matrix adds its intensity after ammonia modified graphene has and significantly promotes, thus has postponed material and existed
The generation of crackle under plus load effect.Meanwhile, the strong cementation between carbon fiber and resin matrix, stop
The further development of crackle.Ammonia modified graphene considerably improves the mechanical property of carbon fibre composite.
3, technique is simple, environmentally safe, is suitable for industrialized production.
4, carbon fiber/graphite alkene/epoxy resin composite material that prepared by the present invention at the addition of Graphene is
During 0.5wt%, mechanical property is optimum, and bending strength reaches 1525.4MPa, and interlaminar shear strength reaches
91.14MPa, compares carbon-fibre reinforced epoxy resin composite material and has been respectively increased 15.41% and 14.14%.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail, but the present invention is not limited to following enforcement
Example.Following example the most every 100ml concentrated sulphuric acid correspondence 1.5gNaNO3Solid, 1.5g graphite, 9g Gao Meng
Acid potassium, consumption also can be adjusted.
Embodiment 1
Weigh NaNO3Solid is dissolved in the concentrated sulphuric acid of 98%, mixed liquor is placed in ice-water bath stirring simultaneously and makes
NaNO3Solid fully dissolves；Weigh a small amount of graphite to join in above-mentioned mixed liquor, stir；Subsequently,
It is slowly added to excess potassium permanganate aoxidize, adition process controls reaction temperature and is less than 20 DEG C, stir
Mix uniformly, temperature is transferred to 30 DEG C and continues stirring reaction；Then in mixed liquor, add deionized water dilute also
Dropping H2O2, make solution become glassy yellow；Filter, with the hydrochloric acid solution of mass concentration 5% while filtering
Washing；The filter cake deionized water dilution obtained after filtering, then carry out ultrasonic and centrifugal treating；After centrifugal
The supernatant obtained adds hydrochloric acid solution, is sufficiently stirred for rear recentrifuge；The lower floor obtained after being centrifuged glues
Property solid dry, obtain graphite oxide sample；Take gained graphite oxide, quickly put into and be preheated to 1050 DEG C
Muffle furnace in keep 30s obtain expanded graphite alkene；Take a certain amount of expanded graphite alkene and add in dehydrated alcohol,
Vacuum drying obtains Graphene.
By Graphene and N, N'-Dicyclohexylcarbodiimide (DCC) is dispersed in amino silicane coupling agent 3-aminopropyl
In triethoxysilane solution, Graphene dispersion concentration in 3-aminopropyl triethoxysilane is
0.5mg/ml, Graphene and N, the mass ratio of N'-Dicyclohexylcarbodiimide (DCC) is 10:3.By mixed liquor
Ultrasonic 1 hour, the homogeneous mixture of black is heated to 60 DEG C, stirs 12 hours, be then centrifuged for separating also
Clean with deionized water, gains are placed in vacuum drying oven at 65 DEG C of dry 12h, obtain ammonia modified graphene；
Epoxy resin, polyurethane-modified liquid rubber, firming agent MDA and amino modified Graphene are pressed
According to the quality of 100:5:25:0.1 than mix homogeneously, mechanical agitation ultrasonic reaction 4h, the asphalt mixtures modified by epoxy resin of every 100 parts
The amount adding accelerator (DMP-30) in fat is 1ml, and continues ultrasonic reaction 1h.Then, by reactant liquor
It is placed in de-bubbled 1h in the vacuum drying oven of 50 DEG C；
Being poured in steeping vat by resin grout liquid, and be placed with supersonic generator in steeping vat, power control is
150W, the T300 level 3K carbon fibre tow of Tuozhan Fiber Co., Ltd., Weihai enters in steeping vat, controls leaching
The glue time is 10 seconds, and tow tension is 150 grams, and the tow after impregnation removes unnecessary resin by spreading roller
Glue, the tow after impregnation is arranged silk by the way of row's silk machine uses winding, is repeatedly wound around 2 layers, at 100 DEG C
Under the conditions of be dried 1h, obtain unidirectional pre-immersion material, in prepreg, carbon fiber mass fraction is 60%.By prepreg
Preparing laminate by flat-bed press press curing, solidify after carrying out in an oven, solidification process is 90 DEG C
Lower solidification 1 hour, then solidifies 2 hours at 130 DEG C, solidifies 2 hours at last 150 DEG C.It is cooled to room
Temperature, obtains carbon fiber/graphite of the present invention alkene/epoxy resin-base composite material.
Embodiment 2
Weigh NaNO3Solid is dissolved in the concentrated sulphuric acid of 98%, mixed liquor is placed in ice-water bath stirring simultaneously and makes
NaNO3Solid fully dissolves；Weigh a small amount of graphite to join in above-mentioned mixed liquor, stir；Subsequently,
It is slowly added to excess potassium permanganate aoxidize, adition process controls reaction temperature and is less than 20 DEG C, stir
Mix uniformly, temperature is transferred to 40 DEG C and continues stirring reaction；Then in mixed liquor, add deionized water dilute also
Dropping H2O2, make solution become glassy yellow；Filter, with the hydrochloric acid solution of mass concentration 5% while filtering
Washing；The filter cake deionized water dilution obtained after filtering, then carry out ultrasonic and centrifugal treating；After centrifugal
The supernatant obtained adds hydrochloric acid solution, is sufficiently stirred for rear recentrifuge；The lower floor obtained after being centrifuged glues
Property solid dry, obtain graphite oxide sample；Take gained graphite oxide, quickly put into and be preheated to 1050 DEG C
Muffle furnace in keep 30s obtain expanded graphite alkene；Take a certain amount of expanded graphite alkene and add in dehydrated alcohol,
Ultrasonic 5h, vacuum drying obtains Graphene.
By Graphene and N, it is molten that N'-Dicyclohexylcarbodiimide (DCC) is dispersed in 3-aminopropyl triethoxysilane
In liquid, Graphene dispersion concentration in 3-aminopropyl triethoxysilane is 2mg/ml, Graphene and N, N'-
The mass ratio of Dicyclohexylcarbodiimide (DCC) is 2:1.By ultrasonic for mixed liquor 3 hours, uniform by black
Mixture is heated to 80 DEG C, stirs 20 hours, is then centrifuged for separating and cleaning with deionized water, by gains
It is placed in vacuum drying oven at 65 DEG C of dry 12h, obtains ammonia modified graphene；By epoxy resin, polyurethane-modified
Liquid rubber, firming agent methyl tetrahydro phthalic anhydride and amino modified Graphene mix according to the mass ratio of 100:15:60:0.1
Close uniformly, mechanical agitation ultrasonic reaction 8h, the epoxy resin of every 100 parts adds accelerator (DMP-30)
Amount be 1ml, and continue ultrasonic reaction 2h.Then, place reaction liquid in the vacuum drying oven of 50 DEG C and deaerate
Bubble 2h；
Being poured in steeping vat by resin grout liquid, and be placed with supersonic generator in steeping vat, power control is
200W, the T300 level 3K carbon fibre tow of Tuozhan Fiber Co., Ltd., Weihai enters in steeping vat, controls leaching
The glue time is 20 seconds, and tow tension is 200 grams, and the tow after impregnation removes unnecessary resin by spreading roller
Glue, the tow after impregnation is arranged silk by the way of row's silk machine uses winding, is repeatedly wound around 4 layers, at 120 DEG C
Under the conditions of be dried 4h, obtain unidirectional pre-immersion material, in prepreg, carbon fiber mass fraction is 60%.By prepreg
Preparing laminate by flat-bed press press curing, solidify after carrying out in an oven, solidification process is 90 DEG C
Lower solidification 2 hours, then solidifies 4 hours at 130 DEG C, solidifies 4 hours at last 150 DEG C.It is cooled to room
Temperature, obtains carbon fiber/graphite of the present invention alkene/epoxy resin-base composite material.
Embodiment 3
Weigh NaNO3Solid is dissolved in the concentrated sulphuric acid of 98%, mixed liquor is placed in ice-water bath stirring simultaneously and makes
NaNO3Solid fully dissolves；Weigh a small amount of graphite to join in above-mentioned mixed liquor, stir；Subsequently,
It is slowly added to excess potassium permanganate aoxidize, adition process controls reaction temperature and is less than 20 DEG C, stir
Mix uniformly, temperature is transferred to 35 DEG C and continues stirring reaction；Then in mixed liquor, add deionized water dilute also
Dropping H2O2, make solution become glassy yellow；Filter, with the hydrochloric acid solution of mass concentration 5% while filtering
Washing；The filter cake deionized water dilution obtained after filtering, then carry out ultrasonic and centrifugal treating；After centrifugal
The supernatant obtained adds hydrochloric acid solution, is sufficiently stirred for rear recentrifuge；The lower floor obtained after being centrifuged glues
Property solid dry, obtain graphite oxide sample；Take gained graphite oxide, quickly put into and be preheated to 1050 DEG C
Muffle furnace in keep 30s obtain expanded graphite alkene；Take a certain amount of expanded graphite alkene and add in dehydrated alcohol,
Ultrasonic 15h, vacuum drying obtains Graphene.
By Graphene and N, it is molten that N'-Dicyclohexylcarbodiimide (DCC) is dispersed in 3-aminopropyl triethoxysilane
In liquid, Graphene dispersion concentration in 3-aminopropyl triethoxysilane is 1mg/ml, Graphene and N, N'-
The mass ratio of Dicyclohexylcarbodiimide (DCC) is 2:1.By ultrasonic for mixed liquor 2 hours, uniform by black
Mixture is heated to 70 DEG C, stirs 16 hours, is then centrifuged for separating and cleaning with deionized water, by gains
It is placed in vacuum drying oven at 65 DEG C of dry 12h, obtains ammonia modified graphene；By epoxy resin, rubber, solidification
Agent methyl tetrahydro phthalic anhydride and amino modified Graphene stir than mix homogeneously, machinery according to the quality of 100:10:70:0.5
Mixing and ultrasonic reaction 6h, the amount adding accelerator (DMP-30) in the epoxy resin of every 100 parts is 1ml,
And continue ultrasonic reaction 2h.Then, de-bubbled 1h in the vacuum drying oven of 50 DEG C is placed reaction liquid into；
Being poured in steeping vat by resin grout liquid, and be placed with supersonic generator in steeping vat, power control is
180W, the T300 level 3K carbon fibre tow of Tuozhan Fiber Co., Ltd., Weihai enters in steeping vat, controls leaching
15 seconds glue time, tow tension is 180 grams, and the tow after impregnation removes unnecessary resin glue by spreading roller
Liquid, the tow after impregnation is arranged silk by the way of row's silk machine uses winding, is repeatedly wound around 3 layers, at 110 DEG C of bars
Being dried 3h under part, obtain unidirectional pre-immersion material, in prepreg, carbon fiber mass fraction is 60%.Prepreg is led to
Crossing flat-bed press press curing and prepare laminate, solidify after carrying out in an oven, solidification process is at 90 DEG C
Solidify 1 hour, then solidify 2 hours at 130 DEG C, solidify 4 hours at last 150 DEG C.It is cooled to room temperature,
Obtain carbon fiber/graphite of the present invention alkene/epoxy resin-base composite material.
Embodiment 4
Weigh NaNO3Solid is dissolved in the concentrated sulphuric acid of 98%, mixed liquor is placed in ice-water bath stirring simultaneously and makes
NaNO3Solid fully dissolves；Weigh a small amount of graphite to join in above-mentioned mixed liquor, stir；Subsequently,
It is slowly added to excess potassium permanganate aoxidize, adition process controls reaction temperature and is less than 20 DEG C, stir
Mix uniformly, temperature is transferred to 35 DEG C and continues stirring reaction；Then in mixed liquor, add deionized water dilute also
Dropping H2O2, make solution become glassy yellow；Filter, with the hydrochloric acid solution of mass concentration 5% while filtering
Washing；The filter cake deionized water dilution obtained after filtering, then carry out ultrasonic and centrifugal treating；After centrifugal
The supernatant obtained adds hydrochloric acid solution, is sufficiently stirred for rear recentrifuge；The lower floor obtained after being centrifuged glues
Property solid dry, obtain graphite oxide sample；Take gained graphite oxide, quickly put into and be preheated to 1050 DEG C
Muffle furnace in keep 30s obtain expanded graphite alkene；Take a certain amount of expanded graphite alkene and add in dehydrated alcohol,
Ultrasonic 15h, vacuum drying obtains Graphene.
By Graphene and N, it is molten that N'-Dicyclohexylcarbodiimide (DCC) is dispersed in 3-aminopropyl triethoxysilane
In liquid, Graphene dispersion concentration in 3-aminopropyl triethoxysilane is 1mg/ml, Graphene and N, N'-
The mass ratio of Dicyclohexylcarbodiimide (DCC) is 2:1.By ultrasonic for mixed liquor 2 hours, uniform by black
Mixture is heated to 70 DEG C, stirs 16 hours, is then centrifuged for separating and cleaning with deionized water, by gains
It is placed in vacuum drying oven at 65 DEG C of dry 12h, obtains ammonia modified graphene；By epoxy resin, rubber, solidification
Agent MDA and amino modified Graphene according to the quality of 100:10:35:0.5 than mix homogeneously, machinery
Stirring ultrasonic reaction 6h, the amount adding accelerator (DMP-30) in the epoxy resin of every 100 parts is 1ml,
And continue ultrasonic reaction 2h.Then, de-bubbled 1h in the vacuum drying oven of 50 DEG C is placed reaction liquid into；
Being poured in steeping vat by resin grout liquid, and be placed with supersonic generator in steeping vat, power control is
180W, the T300 level 3K carbon fibre tow of Tuozhan Fiber Co., Ltd., Weihai enters in steeping vat, controls leaching
The glue time is 15 seconds, and tow tension is 180 grams, and the tow after impregnation removes unnecessary resin by spreading roller
Glue, the tow after impregnation is arranged silk by the way of row's silk machine uses winding, is repeatedly wound around 3 layers, at 110 DEG C
Under the conditions of be dried 3h, obtain unidirectional pre-immersion material, in prepreg, carbon fiber mass fraction is 60%.By prepreg
Preparing laminate by flat-bed press press curing, solidify after carrying out in an oven, solidification process is 90 DEG C
Lower solidification 1 hour, then solidifies 2 hours at 130 DEG C, solidifies 4 hours at last 150 DEG C.It is cooled to room
Temperature, obtains carbon fiber/graphite of the present invention alkene/epoxy resin-base composite material.
Embodiment 5
The present embodiment is from the different of embodiment 1, resin matrix composite epoxy resin, polyurethane-modified
Liquid rubber rubber, firming agent MDA and amino modified Graphene are according to the matter of 100:10:30:0.7
Amount compares mix homogeneously.
Embodiment 6
The present embodiment is from the different of embodiment 1, resin matrix composite epoxy resin, polyurethane-modified
Liquid rubber rubber, firming agent MDA and amino modified Graphene are according to the matter of 100:10:30:1
Amount compares mix homogeneously.
Embodiment 7
The present embodiment is from the different of embodiment 3, resin matrix composite epoxy resin, polyurethane-modified
Liquid rubber rubber, firming agent methyl tetrahydro phthalic anhydride and amino modified Graphene are according to the quality of 100:10:70:0.7
Compare mix homogeneously.
Embodiment 8
The present embodiment is from the different of embodiment 3, resin matrix composite epoxy resin, polyurethane-modified
Liquid rubber rubber, firming agent methyl tetrahydro phthalic anhydride and amino modified Graphene are according to the quality of 100:10:70:1
Compare mix homogeneously.
Comparative example 1
The T300 level 3K carbon fibre tow of Tuozhan Fiber Co., Ltd., Weihai enters in steeping vat, glue according to
Following method preparation: by epoxy resin, rubber, firming agent MDA according to the matter of 100:10:35
Amount ratio mix homogeneously, mechanical agitation ultrasonic reaction 6h, the epoxy resin of every 100 parts adds 1ml and promotes
Agent (DMP-30), and continue ultrasonic reaction 2h, place reaction liquid into de-bubbled 1h in the vacuum drying oven of 50 DEG C,
Glue is poured into steeping vat, and the power of supersonic generator controls to be 200W, and the control impregnation time is 20 seconds,
Tow tension is 180 grams, and the tow after impregnation removes unnecessary resin adhesive liquid by spreading roller, the silk after impregnation
Restraint and arrange silk by the way of row's silk machine uses winding, be repeatedly wound around 2 layers, under the conditions of 110 DEG C, be dried 3h,
To unidirectional pre-immersion material, in prepreg, carbon fiber mass fraction is 60%.Prepreg is suppressed by flat-bed press
Laminate is prepared in solidification, solidifies after carrying out in an oven, and solidification process is solidification 1 hour at 90 DEG C, then
Solidify 2 hours at 130 DEG C, solidify 2 hours at last 150 DEG C.It is cooled to room temperature, obtains the present embodiment institute
The carbon fiber/epoxy resin composite material stated.
Comparative example 2
The T300 level 3K carbon fibre tow of Tuozhan Fiber Co., Ltd., Weihai enters in steeping vat, glue according to
Following method preparation: by epoxy resin, rubber, firming agent methyl tetrahydro phthalic anhydride according to the quality of 100:15:70
Ratio mix homogeneously, mechanical agitation ultrasonic reaction 6h, add 1ml accelerator in the epoxy resin of every 100 parts
(DMP-30), and continue ultrasonic reaction 2h, place reaction liquid into de-bubbled 1h in the vacuum drying oven of 50 DEG C,
Glue is poured into steeping vat, and the power of supersonic generator controls to be 180W, and the control impregnation time is 15 seconds,
Tow tension is 180 grams, and the tow after impregnation removes unnecessary resin adhesive liquid by spreading roller, the silk after impregnation
Restraint and arrange silk by the way of row's silk machine uses winding, be repeatedly wound around 4 layers, under the conditions of 110 DEG C, be dried 3h,
To unidirectional pre-immersion material, in prepreg, carbon fiber mass fraction is 60%.Prepreg is suppressed by flat-bed press
Laminate is prepared in solidification, solidifies after carrying out in an oven, and solidification process is solidification 1 hour at 90 DEG C, then
Solidify 2 hours at 130 DEG C, solidify 2 hours at last 150 DEG C.It is cooled to room temperature, obtains the present embodiment institute
The carbon fiber/epoxy resin composite material stated.
The present invention tests carbon according to " GB/T 1449-2005 fibre reinforced plastics bending property test method "
The bending property of fibrous composite, according to " JC/T 773 unidirectional fibre reinforced plastics interlayer shear strength is tried
Proved recipe method " test the interlaminar shear strength of carbon fibre composite, the embodiment of the present invention 1～8 and comparative example
The mechanical experimental results of 1～2 carbon fibre composites obtained is as shown in table 1.
The mechanical performance data of the carbon fibre composite that table 1 embodiment of the present invention and comparative example obtain
| Sample | Bending strength (MPa) | Interlaminar shear strength (MPa) |
| Embodiment 1 | 1365.5 | 87.33 |
| Embodiment 2 | 1433.8 | 87.11 |
| Embodiment 3 | 1525.4 | 91.14 |
| Embodiment 4 | 1460.1 | 88.24 |
| Embodiment 5 | 1420.3 | 86.06 |
| Embodiment 6 | 1391.9 | 86.47 |
| Embodiment 7 | 1402.6 | 85.59 |
| Embodiment 8 | 1396.4 | 85.38 |
| Comparative example 1 | 1321.7 | 79.85 |
| Comparative example 2 | 1315.2 | 79.92 |
As can be seen from Table 1, the bending of the carbon fiber/graphite alkene/epoxy resin composite material obtained in the present invention
Intensity compares carbon fiber/epoxy resin composite material with interlaminar shear strength significant raising, and modification is described
There was added of Graphene helps uniformly transferring of plus load, and the interface binding power between carbon fiber and resin matrix is relatively
Good, contribute to the raising of mechanical property.
Finally should be noted that: above example is only in order to make further technical scheme
Bright, but be not limited thereto, after those skilled in the art read description of the invention, can be to the tool of the present invention
Body embodiment is modified or equivalent, these without departing from spirit and scope of the invention any amendment or
Person's equivalent, all within the claims that application is awaited the reply.
Claims (10)
1. the preparation method of carbon fiber/graphite alkene/epoxy prepreg, it is characterised in that comprise the following steps successively:
(1) preparation of Graphene
(2) by Graphene and N, N'-Dicyclohexylcarbodiimide (DCC) is dispersed in amino silicane coupling agent solution, will mixing
Ultrasonic 1～3 hour of liquid, is heated to 60～80 DEG C by the homogeneous mixture of black, stirs 12～20 hours, is then centrifuged for separating also
Clean with deionized water, gains are placed in vacuum drying oven and are dried, obtain ammonia modified graphene；
(3) the ammonia modified graphene of gained in step (2) is joined epoxy resin, polyurethane-modified liquid rubber and solidification
In agent composition system, mechanical agitation ultrasonic reaction 4～8h, add accelerator (DMP-30), and continue ultrasonic reaction 1～2h；
Then, de-bubbled in vacuum drying oven is placed reaction liquid into；Obtain Graphene/epoxy resin serosity；
(4) Graphene obtained above/epoxy resin serosity is poured in steeping vat, and in steeping vat, be placed with ultrasound wave send out
Raw device, then immerses in steeping vat by carbon fibre tow, and the tow after impregnation removes unnecessary resin adhesive liquid by spreading roller, leaching
Tow after glue arranges silk by the way of row's silk machine uses winding, is repeatedly wound around, and is dried 1～4h under the conditions of 100～120 DEG C,
Obtain unidirectional carbon/Graphene/epoxy prepreg.
2. according to the preparation method of a kind of carbon fiber/graphite alkene/epoxy prepreg described in claim 1, it is characterised in that
The preparation of Graphene: weigh NaNO3Solid is dissolved in the concentrated sulphuric acid of 98%, mixed liquor is placed in ice-water bath stirring simultaneously and makes
NaNO3Solid fully dissolves；Weigh graphite to join in above-mentioned mixed liquor, stir；Subsequently, excess it is slowly added to high
Potassium manganate aoxidizes, and controls reaction temperature and is less than 20 DEG C, stir, temperature is transferred to 30-40 DEG C in adition process
Continue stirring reaction；Then in mixed liquor, add deionized water dilute and drip H2O2, make solution become glassy yellow；Filter,
With the hydrochloric acid solution washing of mass concentration 5% while filtering, remove the MnO in solution2；The filter cake obtained after filtering is used
Deionized water dilutes, then carries out ultrasonic and centrifugal treating；The supernatant obtained after centrifugal adds hydrochloric acid solution, fully stirs
Mix rear recentrifuge；The lower floor's viscous solid obtained after being centrifuged is dried, and obtains graphite oxide sample；Take gained graphite oxide,
Quickly put into and be preheated in the Muffle furnace of 1050 DEG C keep 30s to obtain expanded graphite alkene；Take expanded graphite alkene and add anhydrous second
In alcohol, ultrasonic stripping is not higher than 15h, and vacuum drying obtains Graphene.
3. according to the preparation method of a kind of carbon fiber/graphite alkene/epoxy prepreg described in claim 2, it is characterised in that
Described in above-mentioned steps (1), graphite is natural flake graphite, and Graphene is single or multiple lift Graphene.
4. according to the preparation method of a kind of carbon fiber/graphite alkene/epoxy prepreg described in claim 1, it is characterised in that
Amino silicane coupling agent described in step (2) is 3-aminopropyl triethoxysilane, and Graphene is at 3-aminopropyl-triethoxy
Dispersion concentration in silane is 0.5～2mg/ml.
5. according to the preparation method of a kind of carbon fiber/graphite alkene/epoxy prepreg described in claim 1, it is characterised in that
Graphene and N, the mass ratio of N'-Dicyclohexylcarbodiimide (DCC) is 10:3～5.
6. according to the preparation method of a kind of carbon fiber/graphite alkene/epoxy prepreg described in claim 1, it is characterised in that
In step (3), in composition system, firming agent is MDA or methyl tetrahydro phthalic anhydride, and accelerator is 2,4,6-tri-(two
Methylamino methyl) phenol；Each constituent mass ratio epoxy resin in composition system: polyurethane-modified liquid rubber: firming agent two
Diaminodiphenylmethane is 100:5～15:25～40, or epoxy resin: polyurethane-modified liquid rubber: firming agent methyl tetrahydro phthalic anhydride
For 100:5～15:60～70, the amount adding accelerator in the epoxy resin of every 100 parts is 1ml.
7. according to the preparation method of a kind of carbon fiber/graphite alkene/epoxy prepreg described in claim 1, it is characterised in that
Quality is epoxy resin quality 0.05～1% of ammonia modified graphene described in step (3)；Epoxy resin is preferably asphalt mixtures modified by epoxy resin
Fat E51.
8. according to the preparation method of a kind of carbon fiber/graphite alkene/epoxy prepreg described in claim 1, it is characterised in that
The operating power of step (4) supersonic generator is 150～200 watts, and the control impregnation time is 10～20 seconds, and tow tension is
150～200 grams.
9. utilize the preparation method of carbon fiber/graphite alkene/epoxy prepreg that claim 1-8 any one method prepares
The method preparing carbon fibre composite, it is characterised in that prepreg is prepared laminate by flat-bed press press curing,
Solidify after carrying out in an oven, be cooled to room temperature, obtain ammonia modified graphene-carbon fiber reinforced epoxy resin-based composite i.e. carbon
Fiber/Graphene/epoxy resin composite material.
10. according to the preparation method of claim 8, it is characterised in that solidification process is solidification 1～2 hour at 90 DEG C, then
Solidify 2～4 hours at 130 DEG C, solidify 2～4 hours at last 150 DEG C.
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