CN109608668A - A kind of preparation of carbon fiber/graphene oxide/epoxy prepreg and carbon fibre composite - Google Patents
A kind of preparation of carbon fiber/graphene oxide/epoxy prepreg and carbon fibre composite Download PDFInfo
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- CN109608668A CN109608668A CN201811467147.6A CN201811467147A CN109608668A CN 109608668 A CN109608668 A CN 109608668A CN 201811467147 A CN201811467147 A CN 201811467147A CN 109608668 A CN109608668 A CN 109608668A
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- 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
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
- C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
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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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/205—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase
- C08J3/21—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase
- C08J3/215—Compounding polymers with additives, e.g. colouring in the presence of a continuous liquid phase the polymer being premixed with a liquid phase at least one additive being also premixed with a liquid phase
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- 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
- C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
- C08J5/10—Reinforcing macromolecular compounds with loose or coherent fibrous material characterised by the additives used in the polymer mixture
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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
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/042—Graphene or derivatives, e.g. graphene oxides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
Abstract
The preparation of a kind of carbon fiber/graphene oxide/epoxy prepreg and carbon fibre composite, is related to technical field of composite materials.The present invention prepares graphene oxide by improved Hummers method, then graphene oxide is transferred in epoxy resin from aqueous solution, improve the dispersibility of graphene oxide in the epoxy, and then the interfacial adhesion of reinforced epoxy and carbon fiber, improve the mechanical property of epoxy resin base carbon fiber composite material.For carbon fiber/graphene oxide/epoxy resin composite material prepared by the present invention when additive amount is 0.5wt%, bending strength reaches 1422.26MPa, improves 20.05% compared to carbon-fibre reinforced epoxy resin composite material；When additive amount is 0.3wt%, interlaminar shear strength has reached 84.67MPa, improves 16.74% compared to carbon-fibre reinforced epoxy resin composite material.
Description
Technical field
The present invention relates to a kind of preparation of composite material, in particular to a kind of unidirectional carbon fiber/graphene oxide/epoxy
The preparation of resin prepreg material and carbon fibre composite.
Background technique
Carbon fibre composite is due to excellent physical and chemical performance, mechanical performance and thermal property, increasingly by people
Concern, be widely used in communicating automobile, sports equipment, aerospace, the fields such as defence and military.Epoxy resin is as carbon
Fibrous composite apply most matrixes, have excellent adhesion, corrosion resistant candle property and chemical stability, but because its own knot
Structure determines that after epoxy resin cure, the associativity of solidfied material and carbon fiber is poor, and the brittleness of material is larger.
Composite material reinforcement body is in conjunction with basal body interface and reinforcement dispersion in the base is influences composite material
An important factor for energy.Multi-scale enhancement carbon fibre composite is a kind of more commonly used means, i.e., be added wherein it is a kind of or
A variety of nano materials.Graphene belongs to typical bi-dimensional cellular shape carbon network structure, the interior carbon by periodically closely arranging of plane
Hexatomic ring is constituted, and is connected between each carbon atom by sp2 hybridized orbit, is had in conductive, toughening and thermally conductive aspect aobvious
The effect of work has positive effect for enhancing carbon fiber epoxy resin composite material.
Compared with graphene, structure and the graphene of graphene oxide are substantially the same, more oxygen-containing functional groups, tool in level
There are better wetability and surface-active.By the method for phase transfer, graphene oxide can be transferred to well ring from water
In oxygen resin, achieve the purpose that it is evenly dispersed, composite material obtained have better performance.
Summary of the invention
In order to obtain more excellent performance of carbon fiber enhancement resin base composite material, carbon is prepared the present invention provides a kind of
The method of fiber/graphene oxide/epoxy prepreg and carbon fibre composite
To achieve the above object, the invention adopts the following technical scheme:
It is a kind of to prepare carbon fiber/graphene oxide/epoxy prepreg, successively the following steps are included:
Step 1: the preparation of graphene oxide
It is preferred that: weigh NaNO3Solid is dissolved in 98% concentrated sulfuric acid, is then placed in magnetic agitation in ice-water bath, is made NaNO3
Solid sufficiently dissolves；It weighs graphite to be added in mixed liquor, stir 15 minutes；Potassium permanganate is weighed, is slowly added within 5-10 minutes
Into mixed liquor, stirs 20 minutes, be maintained at 20 DEG C hereinafter, gradually rising in rear 10 minutes temperature in this process temperature；It will be warm
Degree is increased to 30-40 DEG C, adds preservative film, continues to be stirred to react 1h；Deionized water is added and is warming up to 95 DEG C or more, sustained response 15
Minute；It continuously adds and is preheating to 50 DEG C of deionized water in advance, terminate reaction 30% hydrogen peroxide is added, solution becomes bright orange
Color；Then heat is starched into centrifugal filtration, and is washed with dilute hydrochloric acid (such as 5% dilute hydrochloric acid) solution, centrifugation is precipitated；Take out precipitating
Deionized water is added in object, carries out ultrasound and centrifugal treating again, dilute hydrochloric acid then is added in the supernatant liquor after centrifugation, sufficiently
It is centrifuged, is precipitated again after stirring；65 DEG C of oven drying 36h, obtain graphene oxide.
Step 2: graphene oxide is dissolved in water, ultrasonic 1-3h；By epoxy resin and consisting of phase-transferring agent triglycidyl group pair
Amino-phenol mixing, ultrasonic 1-3h；Then graphene oxide water solution is poured into epoxy resin mixed liquor, room temperature glass bar
Stirring 10-30 minutes, is transferred to graphene oxide in resin, pours out the water on upper layer, 60-80 DEG C of stirring 6-10h；Vacuum drying oven
Dry 8-12h, obtains the mixed liquor of graphene oxide and epoxy resin；
Step 3: curing agent being added in the graphene oxide of step 2 and the mixed liquor of epoxy resin, ultrasound or stir
0.5-1.5h is mixed, promotor is added, continues ultrasound a period of time, mixed liquor is then placed in vacuum drying oven de-bubbled, is obtained
Graphene oxide/epoxy resin sizing liquor.
Step 4: graphene oxide obtained above/epoxy resin sizing liquor is poured into steeping vat, and in steeping vat
Supersonic generator is placed, carbon fiber is immersed in graphene oxide/epoxy resin sizing liquor, passes through one after the completion of impregnation
Lick roller removes extra sizing liquor；
Step 5: the tow after impregnation arranges silk in such a way that row's silk machine is using winding, is wound layer 2-4 repeatedly,
Dry 1~4h, forms unidirectional carbon fiber/graphene oxide/epoxy prepreg under the conditions of 100~120 DEG C.
The preparation of further carbon fibre composite is the following steps are included: step 6: by Unidirectional obtained in step 5
Fiber/graphene oxide/epoxy prepreg prepares laminate by flat-bed press press curing, after carrying out in an oven
Solidification, is cooled to room temperature, and obtains graphene oxide enhancing carbon fiber epoxy based composites i.e. carbon fiber/graphite oxide
Alkene/epoxy resin composite material.
Preferably, graphite described in above-mentioned steps one is natural flake graphite, and graphene oxide is single-layer or multi-layer.
Preferably, the model E51 of epoxy resin described in above-mentioned steps two, the concentration of graphene oxide in water are
1-7mg/ml。
Preferably, curing agent is selected from methyl tetrahydro phthalic anhydride (MeTHPA), diaminodiphenylsulfone (DDS) in above-mentioned steps three,
Promotor is selected from 2,4,6- tri- (dimethylamino methyl) phenol, Boron Trifluoride Ethylamine (BF3MEA.
Preferably, in composition system each component quality than epoxy resin: consisting of phase-transferring agent: curing agent: promotor 80:
10-30:60-80:1-3, preferably 80:20:70:1；Or 80:10-30:30-50:1-3, preferably 80:20:30:3.
Preferably, the quality of graphene oxide is the 0-1.2% of epoxy resin and consisting of phase-transferring agent total amount, does not include 0, preferably
0.1%-0.7%.
Preferably, composite material solidification process described in step 5 is first to solidify 1~2 hour at 90 DEG C, then 130
Solidify at DEG C 2~4 hours, finally solidifies 2~4 hours at 150 DEG C；Or solidify 1~2 hour at 120 DEG C, then exist
Solidify at 150 DEG C 2~4 hours, finally solidifies 2~4 hours at 180 DEG C.Compared with prior art, technology provided by the invention
Scheme has following excellent effect:
1, the present invention makes graphene oxide from aqueous solution by a kind of consisting of phase-transferring agent triglycidyl group para-aminophenol
It is transferred in resin, has achieved the purpose that evenly dispersed, method is simple, green non-pollution.
2, carbon fiber/graphene oxide/epoxy resin composite material prepared by the present invention is in graphene oxide additive amount
When 0.5wt%, bending strength reaches 1422.26MPa, improves 20.05% compared to carbon-fibre reinforced epoxy resin composite material；
When graphene oxide additive amount is 0.3wt%, interlaminar shear strength reaches
84.67MPa improves 16.74% compared to carbon-fibre reinforced epoxy resin composite material.
Specific embodiment
Below by embodiment, the present invention is described in further detail, but the present invention is not limited to following embodiments.
Embodiment 1
It weighs 1.5g NaNO3 solid to be dissolved in the concentrated sulfuric acid that 69ml concentration is 98%, mixed liquor is put into ice-water bath,
Magnetic agitation dissolves NaNO3 solid sufficiently；It weighs 3g natural graphite to be added in mixed liquor, stir 15 minutes；Weigh 9g high
Potassium manganate is slowly added into mixed liquor for 5 minutes, is stirred 20 minutes, is maintained at 20 DEG C hereinafter, at latter 10 points in this process temperature
Clock temperature gradually rises；Temperature is increased to 35 DEG C, adds preservative film, continues to be stirred to react 1h；The heating of 138ml deionized water is added
To 95 DEG C or more, sustained response 15 minutes；It continuously adds and is preheating to 50 DEG C of 420ml deionized water in advance, 30ml is bis- being added
Oxygen water terminates reaction, and solution becomes glassy yellow；Then heat is starched into centrifugal filtration, and is washed with 5% dilute hydrochloric acid solution, is centrifuged
To precipitating；Sediment is taken out, deionized water is added, ultrasound and centrifugal treating are carried out again, then by the supernatant liquor after centrifugation
Dilute hydrochloric acid is added, is centrifuged, is precipitated again after being sufficiently stirred；65 DEG C of oven drying 36h, obtain graphene oxide.
Graphene oxide, that is, 0.05g that mass ratio is 0.1% is dissolved in 50ml water, ultrasonic 1h；By 40g epoxy resin with
The mixing of 10g consisting of phase-transferring agent triglycidyl group para-aminophenol, ultrasonic 1h.Then graphene oxide water solution is poured into epoxy
In resin mixture liquor, room temperature glass bar is stirred 10 minutes, is transferred to graphene oxide in resin, pours out the water on upper layer, and 60 DEG C
Stir 8h.The dry 12h of 80 DEG C of vacuum drying ovens, obtains the mixed liquor of graphene oxide and epoxy resin；
35g curing agent methyl tetrahydro phthalic anhydride is added in mixed liquor, 0.5g promotor 2,4,6- is added in ultrasound 30 minutes
Three (dimethylamino methyl) phenol, continue ultrasound 30 minutes, and mixed liquor is then placed in vacuum drying oven de-bubbled 30 minutes, is obtained
To graphene oxide/epoxy resin sizing liquor, whole system component epoxy: consisting of phase-transferring agent: curing agent: promotor 80:
20:70:1；
Graphene oxide obtained above/epoxy resin sizing liquor is poured into steeping vat, and places and surpasses in steeping vat
Sonic generator, control operating power is in 150W, and the control impregnation time is 10s, and tow tension is 180 grams, by T700 grades of 12K carbon
Fiber is immersed in graphene oxide/epoxy resin sizing liquor, is passed through a lick roller after the completion of impregnation and is removed extra starching
Liquid；
Tow after impregnation arranges silk in such a way that row's silk machine is using winding, winds 3 layers repeatedly, does under the conditions of 120 DEG C
Dry 4h, obtains unidirectional pre-immersion material；Prepreg is prepared into laminate by flat-bed press press curing, it is solid after carrying out in an oven
Change, solidification process be solidify 1h, 2h, 2h respectively under the conditions of 90 DEG C, 130 DEG C, 150 DEG C, be cooled to room temperature, obtain carbon fiber/
Graphene oxide/epoxy resin composite material.
Embodiment 2
It weighs 1.5g NaNO3 solid to be dissolved in the concentrated sulfuric acid that 69ml concentration is 98%, mixed liquor is put into ice-water bath,
Magnetic agitation dissolves NaNO3 solid sufficiently；It weighs 3g natural graphite to be added in mixed liquor, stir 15 minutes；Weigh Gao Meng
Sour potassium is slowly added into mixed liquor for 5 minutes, is stirred 20 minutes, is maintained at 20 DEG C hereinafter, at latter 10 minutes in this process temperature
Temperature gradually rises；Temperature is increased to 35 DEG C, adds preservative film, continues to be stirred to react 1h；Deionized water is added and is warming up to 95 DEG C
More than, sustained response 15 minutes；It continuously adds and is preheating to 50 DEG C of deionized water in advance, terminate reaction hydrogen peroxide is added, it is molten
Liquid becomes glassy yellow；Then heat is starched into centrifugal filtration, and is washed with 5% dilute hydrochloric acid solution, centrifugation is precipitated；Take out precipitating
Deionized water is added in object, carries out ultrasound and centrifugal treating again, dilute hydrochloric acid then is added in the supernatant liquor after centrifugation, sufficiently
It is centrifuged, is precipitated again after stirring；65 DEG C of oven drying 36h, obtain graphene oxide.
Graphene oxide, that is, 0.15g that mass ratio is 0.3% is dissolved in 50ml water, ultrasonic 1h；By 40g epoxy resin with
The mixing of 10g consisting of phase-transferring agent triglycidyl group para-aminophenol, ultrasonic 1h.Then graphene oxide water solution is poured into epoxy
In resin mixture liquor, room temperature glass bar is stirred 10 minutes, is transferred to graphene oxide in resin, pours out the water on upper layer, and 60 DEG C
Stir 8h.The dry 12h of 80 DEG C of vacuum drying ovens, obtains the mixed liquor of graphene oxide and epoxy resin；
35g curing agent methyl tetrahydro phthalic anhydride is added in mixed liquor, 0.5g promotor 2,4,6- is added in ultrasound 30 minutes
Three (dimethylamino methyl) phenol, continue ultrasound 30 minutes, and mixed liquor is then placed in vacuum drying oven de-bubbled 30 minutes, is obtained
To graphene oxide/epoxy resin sizing liquor, whole system component epoxy: consisting of phase-transferring agent: curing agent: promotor 80:
20:70:1；
Graphene oxide obtained above/epoxy resin sizing liquor is poured into steeping vat, and places and surpasses in steeping vat
Sonic generator, control operating power is in 150W, and the control impregnation time is 10s, and tow tension is 180 grams, by T700 grades of 12K carbon
Fiber is immersed in graphene oxide/epoxy resin sizing liquor, is passed through a lick roller after the completion of impregnation and is removed extra starching
Liquid；
Tow after impregnation arranges silk in such a way that row's silk machine is using winding, winds 3 layers repeatedly, does under the conditions of 120 DEG C
Dry 4h, obtains unidirectional pre-immersion material；Prepreg is prepared into laminate by flat-bed press press curing, it is solid after carrying out in an oven
Change, solidification process be solidify 1h, 2h, 2h respectively under the conditions of 90 DEG C, 130 DEG C, 150 DEG C, be cooled to room temperature, obtain carbon fiber/
Graphene oxide/epoxy resin composite material.
Embodiment 3
It weighs 1.5g NaNO3 solid to be dissolved in the concentrated sulfuric acid that 69ml concentration is 98%, mixed liquor is put into ice-water bath,
Magnetic agitation dissolves NaNO3 solid sufficiently；It weighs 3g natural graphite to be added in mixed liquor, stir 15 minutes；Weigh Gao Meng
Sour potassium is slowly added into mixed liquor for 5 minutes, is stirred 20 minutes, is maintained at 20 DEG C hereinafter, at latter 10 minutes in this process temperature
Temperature gradually rises；Temperature is increased to 35 DEG C, adds preservative film, continues to be stirred to react 1h；Deionized water is added and is warming up to 95 DEG C
More than, sustained response 15 minutes；It continuously adds and is preheating to 50 DEG C of deionized water in advance, terminate reaction hydrogen peroxide is added, it is molten
Liquid becomes glassy yellow；Then heat is starched into centrifugal filtration, and is washed with 5% dilute hydrochloric acid solution, centrifugation is precipitated；Take out precipitating
Deionized water is added in object, carries out ultrasound and centrifugal treating again, dilute hydrochloric acid then is added in the supernatant liquor after centrifugation, sufficiently
It is centrifuged, is precipitated again after stirring；65 DEG C of oven drying 36h, obtain graphene oxide.
Graphene oxide, that is, 0.25g that mass ratio is 0.5% is dissolved in 50ml water, ultrasonic 2h；By 40g epoxy resin with
The mixing of 10g consisting of phase-transferring agent triglycidyl group para-aminophenol, ultrasonic 1h.Then graphene oxide water solution is poured into epoxy
In resin mixture liquor, room temperature glass bar is stirred 10 minutes, is transferred to graphene oxide in resin, pours out the water on upper layer, and 60 DEG C
Stir 8h.The dry 12h of 80 DEG C of vacuum drying ovens, obtains the mixed liquor of graphene oxide and epoxy resin；
35g curing agent methyl tetrahydro phthalic anhydride is added in mixed liquor, 0.5g promotor 2,4,6- is added in ultrasound 30 minutes
Three (dimethylamino methyl) phenol, continue ultrasound 30 minutes, and mixed liquor is then placed in vacuum drying oven de-bubbled 30 minutes, is obtained
To graphene oxide/epoxy resin sizing liquor, whole system component epoxy: consisting of phase-transferring agent: curing agent: promotor 80:
20:70:1；
Graphene oxide obtained above/epoxy resin sizing liquor is poured into steeping vat, and places and surpasses in steeping vat
Sonic generator, control operating power is in 150W, and the control impregnation time is 10s, and tow tension is 180 grams, by T700 grades of 12K carbon
Fiber is immersed in graphene oxide/epoxy resin sizing liquor, is passed through a lick roller after the completion of impregnation and is removed extra starching
Liquid；
Tow after impregnation arranges silk in such a way that row's silk machine is using winding, winds 3 layers repeatedly, does under the conditions of 120 DEG C
Dry 4h, obtains unidirectional pre-immersion material；Prepreg is prepared into laminate by flat-bed press press curing, it is solid after carrying out in an oven
Change, solidification process be solidify 1h, 2h, 2h respectively under the conditions of 90 DEG C, 130 DEG C, 150 DEG C, be cooled to room temperature, obtain carbon fiber/
Graphene oxide/epoxy resin composite material.
Embodiment 4
It weighs 1.5g NaNO3 solid to be dissolved in the concentrated sulfuric acid that 69ml concentration is 98%, mixed liquor is put into ice-water bath,
Magnetic agitation dissolves NaNO3 solid sufficiently；It weighs 3g natural graphite to be added in mixed liquor, stir 15 minutes；Weigh Gao Meng
Sour potassium is slowly added into mixed liquor for 5 minutes, is stirred 20 minutes, is maintained at 20 DEG C hereinafter, at latter 10 minutes in this process temperature
Temperature gradually rises；Temperature is increased to 35 DEG C, adds preservative film, continues to be stirred to react 1h；Deionized water is added and is warming up to 95 DEG C
More than, sustained response 15 minutes；It continuously adds and is preheating to 50 DEG C of deionized water in advance, terminate reaction hydrogen peroxide is added, it is molten
Liquid becomes glassy yellow；Then heat is starched into centrifugal filtration, and is washed with 5% dilute hydrochloric acid solution, centrifugation is precipitated；Take out precipitating
Deionized water is added in object, carries out ultrasound and centrifugal treating again, dilute hydrochloric acid then is added in the supernatant liquor after centrifugation, sufficiently
It is centrifuged, is precipitated again after stirring；65 DEG C of oven drying 36h, obtain graphene oxide.
Graphene oxide, that is, 0.35g that mass ratio is 0.7% is dissolved in 50ml water, ultrasonic 3h；By 40g epoxy resin with
The mixing of 10g consisting of phase-transferring agent triglycidyl group para-aminophenol, ultrasonic 1h.Then graphene oxide water solution is poured into epoxy
In resin mixture liquor, room temperature glass bar is stirred 10 minutes, is transferred to graphene oxide in resin, pours out the water on upper layer, and 60 DEG C
Stir 8h.The dry 12h of 80 DEG C of vacuum drying ovens, obtains the mixed liquor of graphene oxide and epoxy resin；
35g curing agent methyl tetrahydro phthalic anhydride is added in mixed liquor, 0.5g promotor 2,4,6- is added in ultrasound 30 minutes
Three (dimethylamino methyl) phenol, continue ultrasound 30 minutes, and mixed liquor is then placed in vacuum drying oven de-bubbled 30 minutes, is obtained
To graphene oxide/epoxy resin sizing liquor, whole system component epoxy: consisting of phase-transferring agent: curing agent: promotor 80:
20:70:1；
Graphene oxide obtained above/epoxy resin sizing liquor is poured into steeping vat, and places and surpasses in steeping vat
Sonic generator, control operating power is in 150W, and the control impregnation time is 10s, and tow tension is 180 grams, by T700 grades of 12K carbon
Fiber is immersed in graphene oxide/epoxy resin sizing liquor, is passed through a lick roller after the completion of impregnation and is removed extra starching
Liquid；
Tow after impregnation arranges silk in such a way that row's silk machine is using winding, winds 3 layers repeatedly, does under the conditions of 120 DEG C
Dry 4h, obtains unidirectional pre-immersion material；Prepreg is prepared into laminate by flat-bed press press curing, it is solid after carrying out in an oven
Change, solidification process be solidify 1h, 2h, 2h respectively under the conditions of 90 DEG C, 130 DEG C, 150 DEG C, be cooled to room temperature, obtain carbon fiber/
Graphene oxide/epoxy resin composite material.
Embodiment 5
The present embodiment difference from example 1 is that, the curing agent used in the present embodiment is diamino hexichol
Sulfone (DDS), promotor are Boron Trifluoride Ethylamine (BF3MEA), epoxy resin: consisting of phase-transferring agent: curing agent: promotor 80:
20:30:3, solidification process are to solidify 1h, 2h, 2h respectively under the conditions of 120 DEG C, 150 DEG C, 180 DEG C
Embodiment 6
The present embodiment and embodiment 2 the difference is that, the curing agent used in the present embodiment is diamino hexichol
Sulfone (DDS), promotor are Boron Trifluoride Ethylamine (BF3MEA), epoxy resin: consisting of phase-transferring agent: curing agent: promotor 80:
20:30:3, solidification process are to solidify 1h, 2h, 2h respectively under the conditions of 120 DEG C, 150 DEG C, 180 DEG C
Embodiment 7
The present embodiment and embodiment 3 the difference is that, the curing agent used in the present embodiment is diamino hexichol
Sulfone (DDS), promotor are Boron Trifluoride Ethylamine (BF3MEA), epoxy resin: consisting of phase-transferring agent: curing agent: promotor 80:
20:30:3, solidification process are to solidify 1h, 2h, 2h respectively under the conditions of 120 DEG C, 150 DEG C, 180 DEG C.
Embodiment 8
The present embodiment and embodiment 4 the difference is that, the curing agent used in the present embodiment is diamino hexichol
Sulfone (DDS), promotor are Boron Trifluoride Ethylamine (BF3MEA), epoxy resin: consisting of phase-transferring agent: curing agent: promotor 80:
20:30:3, solidification process are to solidify 1h, 2h, 2h respectively under the conditions of 120 DEG C, 150 DEG C, 180 DEG C.
Comparative example 1
40g epoxy resin is mixed with 10g consisting of phase-transferring agent triglycidyl group para-aminophenol, ultrasonic 1h.
35g curing agent methyl tetrahydro phthalic anhydride is added in mixed liquor, 0.5g promotor 2,4,6- is added in ultrasound 30 minutes
Three (dimethylamino methyl) phenol, continue ultrasound 30 minutes, and mixed liquor is then placed in vacuum drying oven de-bubbled 30 minutes, is obtained
To graphene oxide/epoxy resin sizing liquor；
Graphene oxide obtained above/epoxy resin sizing liquor is poured into steeping vat, and places and surpasses in steeping vat
Sonic generator, control operating power is in 150W, and the control impregnation time is 10s, and tow tension is 180 grams, by T700 grades of 12K carbon
Fiber is immersed in graphene oxide/epoxy resin sizing liquor, is passed through a lick roller after the completion of impregnation and is removed extra starching
Liquid；
Tow after impregnation arranges silk in such a way that row's silk machine is using winding, winds 3 layers repeatedly, does under the conditions of 120 DEG C
Dry 4h, obtains unidirectional pre-immersion material；Prepreg is prepared into laminate by flat-bed press press curing, it is solid after carrying out in an oven
Change, solidification process be solidify 1h, 2h, 2h respectively under the conditions of 90 DEG C, 130 DEG C, 150 DEG C, be cooled to room temperature, obtain carbon fiber/
Graphene oxide/epoxy resin composite material.
Comparative example 2
40g epoxy resin is mixed with 10g consisting of phase-transferring agent triglycidyl group para-aminophenol, ultrasonic 1h.
15g curing agent diaminodiphenylsulfone is added in mixed liquor, 80 DEG C of stirring 1h, it is borontrifluoride that 1.5g promotor is added
Boron mono aminoethane continues to stir 1h, mixed liquor is then placed in vacuum drying oven de-bubbled 30 minutes, obtains graphene oxide/ring
Oxygen resin sizing liquor；
Graphene oxide obtained above/epoxy resin sizing liquor is poured into steeping vat, and places and surpasses in steeping vat
Sonic generator, control operating power is in 150W, and the control impregnation time is 10s, and tow tension is 180 grams, by T700 grades of 12K carbon
Fiber is immersed in graphene oxide/epoxy resin sizing liquor, is passed through a lick roller after the completion of impregnation and is removed extra starching
Liquid；
Tow after impregnation arranges silk in such a way that row's silk machine is using winding, winds 3 layers repeatedly, does under the conditions of 120 DEG C
Dry 4h, obtains unidirectional pre-immersion material；Prepreg is prepared into laminate by flat-bed press press curing, it is solid after carrying out in an oven
Change, solidification process be solidify 1h, 2h, 2h respectively under the conditions of 120 DEG C, 150 DEG C, 180 DEG C, obtain carbon fiber/graphene oxide/
Epoxy resin composite material.
Test
Composite material in whole embodiments and comparative example is cut to required for testing standard using diamond cutter
Size tests the curved of carbon fibre composite according to " GB/T 1449-2005 fibre reinforced plastics bending property test method "
Qu Xingneng tests carbon fibre composite according to " 773 unidirectional fibre reinforced plastics interlayer shear strength test method of JC/T "
Interlaminar shear strength, test result is as shown in table 1.
Table 1
| Sample | Bending strength (MPa) | Interlaminar shear strength (MPa) |
| Embodiment 1 | 1323.63 | 75.79 |
| Embodiment 2 | 1406.54 | 84.67 |
| Embodiment 3 | 1422.26 | 77.02 |
| Embodiment 4 | 1277.64 | 72.71 |
| Embodiment 5 | 1232.13 | 73.48 |
| Embodiment 6 | 1364.35 | 78.16 |
| Embodiment 7 | 1300.71 | 75.24 |
| Embodiment 8 | 1264.92 | 70.05 |
| Comparative example 1 | 1184.72 | 72.53 |
| Comparative example 2 | 1137.64 | 71.84 |
As can be seen from Table 1, carbon fiber/graphene oxide/epoxy resin composite material interlayer that the present invention obtains is cut
Shearing stress, which compares carbon fiber/epoxy resin composite material with bending strength, significant raising, illustrates carbon fiber and resin base
Interface binding power between body is preferable, and the addition of graphene oxide facilitates uniformly transferring for plus load, facilitates mechanical property
Raising.
Finally it should be noted that: above embodiments only to further description of the technical solution of the present invention, but
It is not limited thereto, after those skilled in the art read description of the invention, a specific embodiment of the invention can be carried out
Modification perhaps equivalent replacement these without departing from any modification of spirit and scope of the invention or equivalent replacement, application to
Within the claims criticized.
Claims (10)
1. a kind of carbon fiber/graphene oxide/epoxy prepreg preparation, which comprises the following steps:
Step 1: the preparation of graphene oxide
Step 2: graphene oxide is dissolved in water, ultrasonic 1-3h；By epoxy resin and consisting of phase-transferring agent triglycidyl group to amino
Phenol mixing, ultrasonic 1-3h；Then graphene oxide water solution is poured into epoxy resin mixed liquor, the stirring of room temperature glass bar
It 10-30 minutes, is transferred to graphene oxide in resin, pours out the water on upper layer, 60-80 DEG C of stirring 6-10h；Vacuum drying oven is dry
8-12h obtains the mixed liquor of graphene oxide and epoxy resin；
Step 3: curing agent being added in the graphene oxide of step 2 and the mixed liquor of epoxy resin, ultrasound or stirring
Promotor is added in 0.5-1.5h, continues ultrasound a period of time, mixed liquor is then placed in vacuum drying oven de-bubbled, obtains oxygen
Graphite alkene/epoxy resin sizing liquor.
Step 4: graphene oxide obtained above/epoxy resin sizing liquor is poured into steeping vat, and placed in steeping vat
Carbon fiber is immersed in graphene oxide/epoxy resin sizing liquor by supersonic generator, passes through a kiss-coating after the completion of impregnation
Roller removes extra sizing liquor；
Step 5: tow after impregnation arranges silk in such a way that row's silk machine is using winding, is wound layer 2-4 repeatedly, 100~
Dry 1~4h, forms unidirectional carbon fiber/graphene oxide/epoxy prepreg under the conditions of 120 DEG C.
2. a kind of carbon fiber/graphene oxide/epoxy prepreg preparation method described in accordance with the claim 1, special
Sign is, the preparation of graphene oxide: weighs NaNO3Solid is dissolved in 98% concentrated sulfuric acid, is then placed in magnetic force in ice-water bath
Stirring, makes NaNO3Solid sufficiently dissolves；It weighs graphite to be added thereto, stir 15 minutes；Potassium permanganate is weighed, 5-10 minutes slow
It is slow to be added, it stirs 20 minutes, is maintained at 20 DEG C hereinafter, gradually rising in rear 10 minutes temperature in this process temperature；By temperature liter
Height arrives 30-40 DEG C, adds preservative film, continues to be stirred to react 1h；Deionized water is added and is warming up to 95 DEG C or more, sustained response 15 is divided
Clock；It continuously adds and is preheating to 50 DEG C of deionized water in advance, terminate reaction 30% hydrogen peroxide is added, solution becomes glassy yellow；
Then heat is starched into centrifugal filtration, and is washed with dilute hydrochloric acid solution, centrifugation is precipitated；Sediment is taken out, deionized water is added, then
Secondary progress ultrasound and centrifugal treating, are then added dilute hydrochloric acid for the supernatant liquor after centrifugation, are centrifuged, obtain again after being sufficiently stirred
Precipitating；65 DEG C of oven drying 36h, obtain graphene oxide.
3. a kind of carbon fiber/graphene oxide/epoxy prepreg preparation method described in accordance with the claim 1, special
Sign is that graphite described in step 1 is natural flake graphite, and graphene oxide is single-layer or multi-layer.
4. a kind of carbon fiber/graphene oxide/epoxy prepreg preparation method described in accordance with the claim 1, special
Sign is, the model E51 of epoxy resin described in step 2；Curing agent is selected from methyl tetrahydro phthalic anhydride in step 3
(MeTHPA), diaminodiphenylsulfone (DDS), promotor are selected from 2,4,6- tri- (dimethylamino methyl) phenol, boron trifluoride list second
Amine (BF3MEA).
5. a kind of carbon fiber/graphene oxide/epoxy prepreg preparation method described in accordance with the claim 1, special
Sign is that the concentration of graphene oxide in water is 1-7mg/ml in step 2.
6. a kind of carbon fiber/graphene oxide/epoxy prepreg preparation method described in accordance with the claim 1, special
Sign is that each component quality is than epoxy resin: consisting of phase-transferring agent: curing agent: promotor 80:10-30:60-80:1-3, preferably
80:20:70:1；Or 80:10-30:30-50:1-3, preferably 80:20:30:3.
7. a kind of carbon fiber/graphene oxide/epoxy prepreg preparation method described in accordance with the claim 1, special
Sign is that it does not include 0 that the quality of graphene oxide, which is the 0-1.2% of epoxy resin and consisting of phase-transferring agent total amount, preferably 0.1%-
0.7%.
8. a kind of carbon fiber/graphene oxide/epoxy resin composite material preparation, which comprises the following steps: packet
The described in any item methods of claim 1-7 are included, further include following steps:
Step 6: unidirectional carbon fiber/graphene oxide/epoxy prepreg obtained in step 5 is passed through into flat-bed press
Press curing prepares laminate, solidifies after carrying out in an oven, is cooled to room temperature, and obtains graphene oxide enhancing carbon fiber epoxy
Polymer matrix composites, that is, carbon fiber/graphene oxide/epoxy resin composite material.
9. according to method for claim 8, which is characterized in that composite material solidification process described in step 5 is first at 90 DEG C
Solidification 1~2 hour, then solidifies 2~4 hours at 130 DEG C, finally solidifies 2~4 hours at 150 DEG C；Or at 120 DEG C
Lower solidification 1~2 hour, then solidifies 2~4 hours at 150 DEG C, finally solidifies 2~4 hours at 180 DEG C.
10. carbon fiber/graphene oxide/epoxy prepreg is prepared according to any one of claim 1-9 the method
Or carbon fiber/graphene oxide/epoxy resin composite material.
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| CN110373001A (en) * | 2019-08-23 | 2019-10-25 | 哈尔滨工业大学 | A kind of preparation method based on graphene enhancing carbon fibre composite |
| CN110396282A (en) * | 2019-08-30 | 2019-11-01 | 西安航空学院 | A kind of method of graphene interface modification carbon fiber/epoxy resin composite material |
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| CN115538170A (en) * | 2022-09-06 | 2022-12-30 | 长春工业大学 | Modified carbon fiber, preparation method and application thereof, and modified carbon fiber epoxy resin composite material |
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