CN105968717A - Preparation of carbon fiber/graphene/carbon nanotube/epoxy resin prepreg and carbon fiber composite material - Google Patents
Preparation of carbon fiber/graphene/carbon nanotube/epoxy resin prepreg and carbon fiber composite material Download PDFInfo
- Publication number
- CN105968717A CN105968717A CN201610339807.7A CN201610339807A CN105968717A CN 105968717 A CN105968717 A CN 105968717A CN 201610339807 A CN201610339807 A CN 201610339807A CN 105968717 A CN105968717 A CN 105968717A
- Authority
- CN
- China
- Prior art keywords
- epoxy resin
- graphene
- carbon fiber
- carbon nano
- graphite alkene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
- C08J2409/00—Characterised by the use of homopolymers or copolymers of conjugated diene hydrocarbons
- C08J2409/02—Copolymers with acrylonitrile
Abstract
The invention relates to preparation of a carbon fiber/graphene/carbon nanotube/epoxy resin prepreg and a carbon fiber composite material, belonging to the field of composite material preparation. The graphene is used for chemical modification, and forms a two-element reinforcing filler with the multiwall carbon nanotubes, thereby being beneficial to the dispersion of the reinforcer in the matrix. The epoxy resin-liquid carboxy nitrile rubber combined matrix is provided, and the multidimensional material is compounded to prepare the continuous carbon fiber composite material, thereby enhancing the mechanical properties of the composite material. When the graphene/carbon nanotube content reaches 1.0 wt%, the interlaminar shear strength reaches 87.90 MPa; and when the graphene/carbon nanotube content reaches 2.0 wt%, the tensile strength reaches 64.31 MPa at the maximum.
Description
Technical field
The present invention relates to a kind of carbon fiber/graphite alkene/carbon nano tube/epoxy resin leaching material and the system of carbon fibre composite
Preparation Method, is specifically related to a kind of method preparing composite for matrix with rubber-composition epoxy resin.
Background technology
Modern development in science and technology is rapid, and composite application in terms of Aero-Space is wider, and people are to multiple simultaneously
The requirement of the performance of condensation material is more and more harsh.Being dispersed into of composite material reinforcement body and basal body interface and reinforcement is multiple
The bottleneck of condensation material performance boost, based on changing the physics of composite material reinforcement body and chemical micro structure across scale Design thought,
The mechanical property that solution interface problem and scattering problem improve composite simultaneously becomes an important research direction.
Material with carbon element such as Graphene, CNT etc. have the mechanical property of excellence, are usually utilized to as reinforcement, but
The hydrophobicity of grapheme material limits it and uses, and by chemical modification, introducing polar group on graphene sheet layer can have
Effect increases the hydrophilic of grapheme material, suppresses it to reunite simultaneously.Material with carbon element is divided into the fullerene of zero dimension, one-dimensional CNT
With the grapheme material of two dimension, the synergism by the material with carbon element of both or three kinds of different dimensions can be in resin matrix
Form network structure, more efficiently transmit load, promote mechanical property.
Carbon fiber epoxy based composites is class research composite widely, introduces in resin matrix
Thermoplastic rubber material can effectively improve the fragility of epoxy resin and increase toughness, is simultaneously introduced modified graphene/carbon nanometer
Pipe is as reinforcement, dispersed in epoxy resin-rubber composition.Different scale ground reinforcement synergism, in difference
Dimension play the effect of transmission load and can effectively promote the mechanical property of carbon fiber epoxy based composites.
Summary of the invention
The carbon fiber enhancement resin base composite material more excellent in order to obtain performance, the invention provides one and prepares carbon
Fiber/graphene/carbon nano-tube/epoxy prepreg and the preparation method of carbon fibre 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/carbon nano tube/epoxy resin prepreg, comprises the following steps successively:
Step one: prepare Graphene
Preferably employ following methods:
Weigh NaNO3Solid is dissolved in 98% concentrated sulphuric acid, is placed in ice-water bath and adds rotor and is stirred continuously, and adds scale
Graphite, continuously stirred 30min, it is slowly added to KMnO4, keep 0 DEG C, continue stirring 30min.Then heat to 35 DEG C, stir 1h；
Add deionized water (as being slowly added in 10min) and then heat to 98 DEG C, keep 15min in this temperature；Add the most pre-
The deionized water of heat to 50 DEG C, adds hydrogen peroxide, terminates reaction, and stirs 10min until no longer producing bubble；Configuration about 5%
Hydrochloric acid solution, join in reaction solution, centrifugal be precipitated；It is precipitated to centrifugal liquid pH=7 with deionized water cyclic washing,
Gained is precipitated lyophilizing and obtains graphene oxide, take gained graphene oxide, quickly put into the Muffle furnace being preheated to 1050 DEG C
Middle holding several seconds expanded graphite alkene；Take a certain amount of expanded graphite alkene and add in dehydrated alcohol, ultrasonic stripping about 15h, obtain stone
Ink alkene；
Step 2: Graphene is dissolved in dimethylformamide and forms the equal of 0.1-1mg/mL (preferably 0.33mg/mL)
Even dispersion liquid, the dimethyl formamide solution of dropping isocyanates, in above-mentioned graphene dispersing solution and continuously stirred, mixes molten
In a nitrogen atmosphere, 75-85 DEG C of reaction 0.5-1.5h (preferably 80 DEG C reaction 1h), then by dimethylformamide washing precipitation for liquid
Several times, the dimethyl formamide solution the continuously stirred holding temperature 55 DEG C that add malonaldehyde in precipitation are reacted a night, finally
By centrifugal, dimethylformamide washs, and vacuum drying obtains modified graphene；
Step 3: preparation epoxy resin (such as E-51), firming agent MeTHPA with the mass ratio of liquid carboxy terminated nitrile rubber are
Resin-the rubbery system of 100:60-80:8-12 (preferably 100:70:11) and epoxy resin (such as E-51), firming agent diaminourea two
Phenylmethane (DDM) and the resin-rubber that mass ratio is 100:30-40:8-12 (preferably 100:35:11) of liquid carboxy terminated nitrile rubber
Colloid system, is subsequently adding multi-walled carbon nano-tubes and modified graphene, the addition quality phase of multi-walled carbon nano-tubes and modified graphene
Deng, weight/mass percentage composition is 0.05wt%-1.0wt%；Then, after mechanical agitation ultrasonic reaction 5-7h, add accelerator
2,4,6-tri-(dimethylamino methyl) phenol (DMP-30), and continue ultrasonic reaction a period of time (such as about one hour)；Subsequently,
Place reaction liquid into and be preheated to de-bubbled at least 0.5h in the vacuum drying oven of 50 DEG C, obtain modified graphene/CNT/epoxy
Resin slurry；
Step 4: modified graphene/carbon nano tube/epoxy resin slurry is poured in steeping vat, and put in steeping vat
Put supersonic generator, carbon fiber is immersed in modified graphene/carbon nano tube/epoxy resin slurry, control operating power and exist
120-170W；The control impregnation time is 8-15s, and tow tension is 160-200 gram, and impregnation is removed by a spreading roller after completing
Unnecessary resin adhesive liquid；
Step 5: the tow after impregnation arranges silk by the way of row's silk machine uses winding, is repeatedly wound around, preferably amounts to
Repeatedly it is wound around 3-5 layer, forms unidirectional prepreg cloth；
Step 6: taken off by prepreg cloth, dries 7-12h under 50-70 DEG C of vacuum condition；Then dry at 100-120 DEG C
4-6h, obtains carbon fiber/graphite alkene/carbon nano tube/epoxy resin prepreg；
In above-mentioned steps two, Graphene: isocyanates: malonaldehyde use magnitude relation 100mg:0.005-0.1mol:0.05-
0.1mol。
Carbon fibre composite, it is characterised in that carbon fiber/graphite alkene/CNT/resin prepreg material is passed through hot pressing
Laminate (if pressure used is 5MPa) prepared by machine, and temperature-rise period is: 90 DEG C, 1h；130 DEG C, 2h；150 DEG C, 2h, then protects
Pressure is cooled to room temperature and obtains carbon fiber/graphite alkene/carbon nano tube/epoxy resin composite material.
One-dimensional CNT can improve the stacking of Graphene, on the one hand so enables to filler and disperses in the base all
Even so that filler forms a good bridge linking effect between matrix and carbon fiber；Another aspect, Graphene and carbon nanometer
The conductive mesh structure formed between pipe, is more beneficial for the raising of composite heat stability.Multiple compared to traditional carbon fiber
Condensation material, the existence of the Nano filling of two kinds of dimensions, not only play the cooperative effect between filler, it is often more important that fill out for two kinds
There is dimensionality effect between material, be conducive to improving the mechanical property of composite.
Compared with immediate prior art, the technical scheme that the present invention provides has a following excellent effect:
When modified graphene and CNT respectively account for epoxy-resin systems content be 0.5wt% time, carbon fiber/graphite
The hot strength of alkene/CNT reinforced epoxy base unidirectional composite material and interlaminar shear strength respectively reach 60.02MPa
And 87.80MPa, compare and be not added with the carbon-fibre reinforced epoxy resin composite material of any filler and be respectively increased 14.1% He
10.1%.When modified graphene and CNT respectively account for epoxy-resin systems content be 1.0wt% time, carbon fiber/graphite alkene/
The hot strength of CNT reinforced epoxy base unidirectional composite material and interlaminar shear strength respectively reach 63.53MPa and
82.17MPa, compares and is not added with the carbon-fibre reinforced epoxy resin composite material of any filler and has been respectively increased 20.7% He
3.0%.
Detailed description of the invention
Below by embodiment, the present invention is described in further detail, but the present invention is not limited to following example.
Embodiment 1
Weigh NaNO3Solid 1.5g, crystalline flake graphite 1.5g, KMnO49g is stand-by, NaNO3Solid is dissolved in 100ml concentrated sulphuric acid
In, it is placed in ice-water bath and adds rotor and be stirred continuously addition native graphite, continuously stirred 30min；It is slowly added to KMnO4, hold
Continuous 0 DEG C, continue stirring 30min.Then heat to 35 DEG C, stir 1h；Add 138ml deionized water (slowly to add in 10min
Enter) then heat to 98 DEG C, keep 15min in this temperature；Add 420ml and be preheating to the deionized water of 50 DEG C in advance, add
43ml hydrogen peroxide, terminates reaction, and stirs 10min until no longer producing bubble；Configuration about 5% hydrochloric acid solution (600ml go from
Sub-water+100ml concentrated hydrochloric acid), join in reaction solution, be centrifuged and be precipitated；It is precipitated to be centrifuged with deionized water cyclic washing
Liquid pH=7, then lyophilizing precipitation obtains graphene oxide, takes gained graphene oxide, quickly puts into and be preheated to 1050 DEG C
Muffle furnace keeps 30s expanded graphite alkene；Take a certain amount of expanded graphite alkene and add in dehydrated alcohol, ultrasonic stripping 15h, obtain stone
Ink alkene；
100mg Graphene is dissolved in the uniform dispersion forming 0.33mg/mL in 300mL dimethylformamide, dropping
The dimethyl formamide solution of 0.01mol isocyanates is in above-mentioned graphene dispersing solution and continuously stirred, and mixed solution is at nitrogen
Under gas atmosphere, temperature 80 DEG C reaction 1h, then by dimethylformamide washing precipitation 2 times, in precipitation, add 0.05mol the third two
The dimethyl formamide solution of aldehyde continuously stirred holding temperature 55 DEG C react a night, finally by centrifugal, and dimethylformamide
Washing, vacuum drying obtains modified graphene；
Preparation epoxy resin (E-51), firming agent (MeTHPA) are 100:70 with the mass ratio of liquid carboxy terminated nitrile rubber:
Resin-the rubber solutions of 11, equal proportion adds the multi-walled carbon nano-tubes of 0.1wt% (0.05wt% respectively) and arrives with modified graphene
In resin system solution.Then, after mechanical agitation ultrasonic reaction 6h, add the accelerator (DMP-30) of 0.6mL, and continue super
Phonoresponse 1h.Subsequently, place reaction liquid into de-bubbled 0.5h in the vacuum drying oven being preheated to 50 DEG C, obtain resin-rubber serosity；
Resin rubber serosity is poured in steeping vat, and in steeping vat, places supersonic generator, control operating power
At 150W；The control impregnation time is 10s, and tow tension is 180 grams, uses Weihai to pass through after expanding T300 level 3K carbon fiber impregnation
Row's silk machine uses the mode being wound around to arrange silk, amounts to and is repeatedly wound around 3 layers, forms unidirectional prepreg cloth, taken off by prepreg cloth, true at 60 DEG C
10h is dried under empty condition.Then at 120 DEG C, dry 5h, obtain carbon fiber/graphite alkene/CNT/resin prepreg material.
By hot press prepared by prepreg laminate, and pressure used is 5MPa, and temperature-rise period is: 90 DEG C, 1h；130
DEG C, 2h；150 DEG C, 2h, then pressurize is cooled to room temperature and obtains carbon fiber/graphite of the present invention alkene/CNT/epoxy
Resin composite materials.
Embodiment 2
Weigh NaNO3Solid 1.5g, crystalline flake graphite 1.5g, KMnO49g is stand-by, NaNO3Solid is dissolved in 100ml concentrated sulphuric acid
In, it is placed in ice-water bath and adds rotor and be stirred continuously addition native graphite, continuously stirred 30min；It is slowly added to KMnO4, hold
Continuous 0 DEG C, continue stirring 30min.Then heat to 35 DEG C, stir 1h；Add 138ml deionized water (slowly to add in 10min
Enter) then heat to 98 DEG C, keep 15min in this temperature；Add 420ml and be preheating to the deionized water of 50 DEG C in advance, add
43ml hydrogen peroxide, terminates reaction, and stirs 10min until no longer producing bubble；Configuration about 5% hydrochloric acid solution (600ml go from
Sub-water+100ml concentrated hydrochloric acid), join in reaction solution, be centrifuged and be precipitated；It is precipitated to be centrifuged with deionized water cyclic washing
Liquid pH=7, then lyophilizing precipitation obtains graphene oxide, takes gained graphene oxide, quickly puts into and be preheated to 1050 DEG C
Muffle furnace keeps 30s expanded graphite alkene；Take a certain amount of expanded graphite alkene and add in dehydrated alcohol, ultrasonic stripping 15h, obtain stone
Ink alkene；
100mg Graphene is dissolved in the uniform dispersion forming 0.33mg/mL in 300mL dimethylformamide, dropping
The dimethyl formamide solution of 0.01mol isocyanates is in above-mentioned graphene dispersing solution and continuously stirred, and mixed solution is at nitrogen
Gas atmosphere at temperatures 80 DEG C reaction 1h, then by dimethylformamide washing precipitation 2 times, adds 0.05mol the third two in precipitation
The dimethyl formamide solution of aldehyde continuously stirred holding temperature 55 DEG C react a night, finally by centrifugal, and dimethylformamide
Washing, vacuum drying obtains modified graphene；
Preparation epoxy resin (E-51), firming agent (MeTHPA) are 100:70 with the mass ratio of liquid carboxy terminated nitrile rubber:
Resin-the rubber solutions of 11, equal proportion adds the multi-walled carbon nano-tubes of 0.5wt% (0.25wt% respectively) and arrives with modified graphene
In resin system solution.Then, after mechanical agitation ultrasonic reaction 6h, add the accelerator (DMP-30) of 0.6mL, and continue super
Phonoresponse 1h.Subsequently, place reaction liquid into de-bubbled 0.5h in the vacuum drying oven being preheated to 50 DEG C, obtain resin-rubber serosity；
Resin rubber serosity is poured in steeping vat, and in steeping vat, places supersonic generator, control operating power
At 150W；The control impregnation time is 10s, and tow tension is 180 grams, uses Weihai to pass through after expanding T300 level 3K carbon fiber impregnation
Row's silk machine uses the mode being wound around to arrange silk, amounts to and is repeatedly wound around 3 layers, forms unidirectional prepreg cloth, taken off by prepreg cloth, true at 60 DEG C
10h is dried under empty condition.Then at 120 DEG C, dry 5h, obtain carbon fiber/graphite alkene/CNT/resin prepreg material.
By hot press prepared by prepreg laminate, and pressure used is 5MPa, and temperature-rise period is: 90 DEG C, 1h；130
DEG C, 2h；150 DEG C, 2h, then pressurize is cooled to room temperature and obtains carbon fiber/graphite of the present invention alkene/CNT/epoxy
Resin composite materials.
Embodiment 3
Weigh NaNO3Solid 1.5g, crystalline flake graphite 1.5g, KMnO49g is stand-by, NaNO3Solid is dissolved in 100ml concentrated sulphuric acid
In, it is placed in ice-water bath and adds rotor and be stirred continuously addition native graphite, continuously stirred 30min；It is slowly added to KMnO4, hold
Continuous 0 DEG C, continue stirring 30min.Then heat to 35 DEG C, stir 1h；Add 138ml deionized water (slowly to add in 10min
Enter) then heat to 98 DEG C, keep 15min in this temperature；Add 420ml and be preheating to the deionized water of 50 DEG C in advance, add
43ml hydrogen peroxide, terminates reaction, and stirs 10min until no longer producing bubble；Configuration about 5% hydrochloric acid solution (600ml go from
Sub-water+100ml concentrated hydrochloric acid), join in reaction solution, be centrifuged and be precipitated；It is precipitated to be centrifuged with deionized water cyclic washing
Liquid pH=7, then lyophilizing precipitation obtains graphene oxide, takes gained graphene oxide, quickly puts into and be preheated to 1050 DEG C
Muffle furnace keeps 30s expanded graphite alkene；Take a certain amount of expanded graphite alkene and add in dehydrated alcohol, ultrasonic stripping 15h, obtain stone
Ink alkene；
100mg Graphene is dissolved in the uniform dispersion forming 0.33mg/mL in 300mL dimethylformamide, dropping
The dimethyl formamide solution of 0.01mol isocyanates is in above-mentioned graphene dispersing solution and continuously stirred, and mixed solution is at nitrogen
Gas atmosphere at temperatures 80 DEG C reaction 1h, then by dimethylformamide washing precipitation 2 times, adds 0.05mol the third two in precipitation
The dimethyl formamide solution of aldehyde continuously stirred holding temperature 55 DEG C react a night, finally by centrifugal, and dimethylformamide
Washing, vacuum drying obtains modified graphene；
Preparation epoxy resin (E-51), firming agent (MeTHPA) are 100:70 with the mass ratio of liquid carboxy terminated nitrile rubber:
Resin-the rubber solutions of 11, equal proportion adds the multi-walled carbon nano-tubes of 1.0wt% (0.5wt% respectively) and arrives with modified graphene
In resin system solution.Then, after mechanical agitation ultrasonic reaction 6h, add the accelerator (DMP-30) of 0.6mL, and continue super
Phonoresponse 1h.Subsequently, place reaction liquid into de-bubbled 0.5h in the vacuum drying oven being preheated to 50 DEG C, obtain resin-rubber serosity；
Resin rubber serosity is poured in steeping vat, and in steeping vat, places supersonic generator, control operating power
At 150W；The control impregnation time is 10s, and tow tension is 180 grams, uses Weihai to pass through after expanding T300 level 3K carbon fiber impregnation
Row's silk machine uses the mode being wound around to arrange silk, amounts to and is repeatedly wound around 3 layers, forms unidirectional prepreg cloth, taken off by prepreg cloth, true at 60 DEG C
10h is dried under empty condition.Then at 120 DEG C, dry 5h, obtain carbon fiber/graphite alkene/CNT/resin prepreg material.
By hot press prepared by prepreg laminate, and pressure used is 5MPa, and temperature-rise period is: 90 DEG C, 1h；130
DEG C, 2h；150 DEG C, 2h, then pressurize is cooled to room temperature and obtains carbon fiber/graphite of the present invention alkene/CNT/epoxy
Resin composite materials.
Embodiment 4
Weigh NaNO3Solid 1.5g, crystalline flake graphite 1.5g, KMnO49g is stand-by, NaNO3Solid is dissolved in 100ml concentrated sulphuric acid
In, it is placed in ice-water bath and adds rotor and be stirred continuously addition native graphite, continuously stirred 30min；It is slowly added to KMnO4, hold
Continuous 0 DEG C, continue stirring 30min.Then heat to 35 DEG C, stir 1h；Add 138ml deionized water (slowly to add in 10min
Enter) then heat to 98 DEG C, keep 15min in this temperature；Add 420ml and be preheating to the deionized water of 50 DEG C in advance, add
43ml hydrogen peroxide, terminates reaction, and stirs 10min until no longer producing bubble；Configuration about 5% hydrochloric acid solution (600ml go from
Sub-water+100ml concentrated hydrochloric acid), join in reaction solution, be centrifuged and be precipitated；It is precipitated to be centrifuged with deionized water cyclic washing
Liquid pH=7, then lyophilizing precipitation obtains graphene oxide, takes gained graphene oxide, quickly puts into and be preheated to 1050 DEG C
Muffle furnace keeps 30s expanded graphite alkene；Take a certain amount of expanded graphite alkene and add in dehydrated alcohol, ultrasonic stripping 15h, obtain stone
Ink alkene；
100mg Graphene is dissolved in the uniform dispersion forming 0.33mg/mL in 300mL dimethylformamide, dropping
The dimethyl formamide solution of 0.01mol isocyanates is in above-mentioned graphene dispersing solution and continuously stirred, and mixed solution is at nitrogen
Gas atmosphere at temperatures 80 DEG C reaction 1h, then by dimethylformamide washing precipitation 2 times, adds 0.05mol the third two in precipitation
The dimethyl formamide solution of aldehyde continuously stirred holding temperature 55 DEG C react a night, finally by centrifugal, and dimethylformamide
Washing, vacuum drying obtains modified graphene；
Preparation epoxy resin (E-51), firming agent (MeTHPA) are 100:70 with the mass ratio of liquid carboxy terminated nitrile rubber:
Resin-the rubber solutions of 11, equal proportion adds the multi-walled carbon nano-tubes of 2.0wt% (1.0wt% respectively) and arrives with modified graphene
In resin system solution.Then, after mechanical agitation ultrasonic reaction 6h, add the accelerator (DMP-30) of 0.6mL, and continue super
Phonoresponse 1h.Subsequently, place reaction liquid into de-bubbled 0.5h in the vacuum drying oven being preheated to 50 DEG C, obtain resin-rubber serosity；
Resin rubber serosity is poured in steeping vat, and in steeping vat, places supersonic generator, control operating power
At 150W；The control impregnation time is 10s, and tow tension is 180 grams, uses Weihai to pass through after expanding T300 level 3K carbon fiber impregnation
Row's silk machine uses the mode being wound around to arrange silk, amounts to and is repeatedly wound around 3 layers, forms unidirectional prepreg cloth, taken off by prepreg cloth, true at 60 DEG C
10h is dried under empty condition.Then at 120 DEG C, dry 5h, obtain carbon fiber/graphite alkene/CNT/resin prepreg material.
By hot press prepared by prepreg laminate, and pressure used is 5MPa, and temperature-rise period is: 90 DEG C, 1h；130
DEG C, 2h；150 DEG C, 2h, then pressurize is cooled to room temperature and obtains carbon fiber/graphite of the present invention alkene/CNT/epoxy
Resin composite materials.
Embodiment 5
The present embodiment is with the difference of embodiment 1, and the matrix of the use in the present embodiment is to add 100 parts of epoxies
Resin (E-51) and 35 parts of firming agent MDAs (DDM), mix homogeneously, be subsequently adding 11 parts of liquid carboxyl butyronitrile rubbers
The matrix liquid that glue mix homogeneously is formed.
Embodiment 6
The present embodiment is with the difference of embodiment 2, and the matrix of the use in the present embodiment is to add 100 parts of epoxies
Resin (E-51) and 35 parts of firming agent MDAs (DDM), mix homogeneously, be subsequently adding 11 parts of liquid carboxyl butyronitrile rubbers
The matrix liquid that glue mix homogeneously is formed.
Embodiment 7
The present embodiment is with the difference of embodiment 3, and the matrix of the use in the present embodiment is to add 100 parts of epoxies
Resin (E-51) and 35 parts of firming agent MDAs (DDM), mix homogeneously, be subsequently adding 11 parts of liquid carboxyl butyronitrile rubbers
The matrix liquid that glue mix homogeneously is formed.
Embodiment 8
The present embodiment is with the difference of embodiment 4, and the matrix of the use in the present embodiment is to add 100 parts of epoxies
Resin (E-51) and 35 parts of firming agent MDAs (DDM), mix homogeneously, be subsequently adding 11 parts of liquid carboxyl butyronitrile rubbers
The matrix liquid that glue mix homogeneously is formed.
Comparative example 1
Weigh NaNO3Solid 1.5g, crystalline flake graphite 1.5g, KMnO49g is stand-by, NaNO3Solid is dissolved in 100ml concentrated sulphuric acid
In, it is placed in ice-water bath and adds rotor and be stirred continuously addition native graphite, continuously stirred 30min；It is slowly added to KMnO4, hold
Continuous 0 DEG C, continue stirring 30min.Then heat to 35 DEG C, stir 1h；Add 138ml deionized water (slowly to add in 10min
Enter) then heat to 98 DEG C, keep 15min in this temperature；Add 420ml and be preheating to the deionized water of 50 DEG C in advance, add
43ml hydrogen peroxide, terminates reaction, and stirs 10min until no longer producing bubble；Configuration about 5% hydrochloric acid solution (600ml go from
Sub-water+100ml concentrated hydrochloric acid), join in reaction solution, be centrifuged and be precipitated；It is precipitated to be centrifuged with deionized water cyclic washing
Liquid pH=7, then lyophilizing precipitation obtains graphene oxide, takes gained graphene oxide, quickly puts into and be preheated to 1050 DEG C
Muffle furnace keeps 30s expanded graphite alkene；Take a certain amount of expanded graphite alkene and add in dehydrated alcohol, ultrasonic stripping 15h, obtain stone
Ink alkene；
100mg Graphene is dissolved in the uniform dispersion forming 0.33mg/mL in 300mL dimethylformamide, dropping
The dimethyl formamide solution of 0.01mol isocyanates is in above-mentioned graphene dispersing solution and continuously stirred, and mixed solution is at nitrogen
Gas atmosphere at temperatures 80 DEG C reaction 1h, then by dimethylformamide washing precipitation 2 times, adds 0.05mol the third two in precipitation
The dimethyl formamide solution of aldehyde continuously stirred holding temperature 55 DEG C react a night, finally by centrifugal, and dimethylformamide
Washing, vacuum drying obtains modified graphene；
Preparation epoxy resin (E-51), firming agent (MeTHPA) are 100:70 with the mass ratio of liquid carboxy terminated nitrile rubber:
Resin-the rubber solutions of 11.Then, after mechanical agitation ultrasonic reaction 6h, add the accelerator (DMP-30) of 0.6mL, and continue
Continuous ultrasonic reaction 1h.Subsequently, place reaction liquid into de-bubbled 0.5h in the vacuum drying oven being preheated to 50 DEG C, obtain resin-rubber
Serosity；
Resin rubber serosity is poured in steeping vat, and in steeping vat, places supersonic generator, control operating power
At 150W；The control impregnation time is 10s, and tow tension is 180 grams, uses Weihai to pass through after expanding T300 level 3K carbon fiber impregnation
Row's silk machine uses the mode being wound around to arrange silk, amounts to and is repeatedly wound around 3 layers, forms unidirectional prepreg cloth, taken off by prepreg cloth, true at 60 DEG C
10h is dried under empty condition.Then at 120 DEG C, dry 5h, obtain carbon fiber/graphite alkene/CNT/resin prepreg material.
By hot press prepared by prepreg laminate, and pressure used is 5MPa, and temperature-rise period is: 90 DEG C, 1h；130
DEG C, 2h；150 DEG C, 2h, then pressurize is cooled to room temperature and obtains carbon fiber/graphite of the present invention alkene/CNT/epoxy
Resin composite materials.
Comparative example 2
Weigh NaNO3Solid 1.5g, crystalline flake graphite 1.5g, KMnO49g is stand-by, NaNO3Solid is dissolved in 100ml concentrated sulphuric acid
In, it is placed in ice-water bath and adds rotor and be stirred continuously addition native graphite, continuously stirred 30min；It is slowly added to KMnO4, hold
Continuous 0 DEG C, continue stirring 30min.Then heat to 35 DEG C, stir 1h；Add 138ml deionized water (slowly to add in 10min
Enter) then heat to 98 DEG C, keep 15min in this temperature；Add 420ml and be preheating to the deionized water of 50 DEG C in advance, add
43ml hydrogen peroxide, terminates reaction, and stirs 10min until no longer producing bubble；Configuration about 5% hydrochloric acid solution (600ml go from
Sub-water+100ml concentrated hydrochloric acid), join in reaction solution, be centrifuged and be precipitated；It is precipitated to be centrifuged with deionized water cyclic washing
Liquid pH=7, then lyophilizing precipitation obtains graphene oxide, takes gained graphene oxide, quickly puts into and be preheated to 1050 DEG C
Muffle furnace keeps 30s expanded graphite alkene；Take a certain amount of expanded graphite alkene and add in dehydrated alcohol, ultrasonic stripping 15h, obtain stone
Ink alkene；
100mg Graphene is dissolved in the uniform dispersion forming 0.33mg/mL in 300mL dimethylformamide, dropping
The dimethyl formamide solution of 0.01mol isocyanates is in above-mentioned graphene dispersing solution and continuously stirred, and mixed solution is at nitrogen
Gas atmosphere at temperatures 80 DEG C reaction 1h, then by dimethylformamide washing precipitation 2 times, adds 0.05mol the third two in precipitation
The dimethyl formamide solution of aldehyde continuously stirred holding temperature 55 DEG C react a night, finally by centrifugal, and dimethylformamide
Washing, vacuum drying obtains modified graphene；
The quality of preparation epoxy resin (E-51), firming agent MDA (DDM) and liquid carboxy terminated nitrile rubber
Than the resin-rubber solutions for 100:35:11.Then, after mechanical agitation ultrasonic reaction 6h, add the accelerator of 0.6mL
, and continue ultrasonic reaction 1h (DMP-30).Subsequently, place reaction liquid into de-bubbled 0.5h in the vacuum drying oven being preheated to 50 DEG C,
Obtain resin-rubber serosity；
Resin rubber serosity is poured in steeping vat, and in steeping vat, places supersonic generator, control operating power
At 150W；The control impregnation time is 10s, and tow tension is 180 grams, uses Weihai to pass through after expanding T300 level 3K carbon fiber impregnation
Row's silk machine uses the mode being wound around to arrange silk, amounts to and is repeatedly wound around 3 layers, forms unidirectional prepreg cloth, taken off by prepreg cloth, true at 60 DEG C
10h is dried under empty condition.Then at 120 DEG C, dry 5h, obtain carbon fiber/graphite alkene/CNT/resin prepreg material.
By hot press prepared by prepreg laminate, and pressure used is 5MPa, and temperature-rise period is: 90 DEG C, 1h；130
DEG C, 2h；150 DEG C, 2h, then pressurize is cooled to room temperature and obtains carbon fiber/graphite of the present invention alkene/CNT/epoxy
Resin composite materials.
Test
Composite in whole embodiments and comparative example use diamond cutter be cut to required for testing standard
Size, according to the hot strength of " GB/T 1447-2005 " standard testing composite, surveys according to " JC/T773-2010 " standard
Examination interlaminar shear strength, test result is as shown in table 1.
This it appears that add the carbon fiber/graphite alkene/CNT/ring of modified graphene/CNT from table
Hot strength and the interlaminar shear strength of epoxy resin composite material are higher than comparative example, and comparative example is not add modified graphene/carbon
Nanotube carbon fiber resin matrix composite.Indicate the material with carbon element of addition modified graphene/many sizes of CNT compound
Material matrix can effectively be transmitted load, improve the mechanical property of composite.
Table 1
| Sample | Hot strength (MPa) | Interlaminar shear strength (MPa) |
| Embodiment 1 | 51.97 | 81.28 |
| Embodiment 2 | 55.91 | 83.63 |
| Embodiment 3 | 60.02 | 87.80 |
| Embodiment 4 | 63.53 | 82.17 |
| Embodiment 5 | 52.79 | 82.01 |
| Embodiment 6 | 56.71 | 84.35 |
| Embodiment 7 | 60.82 | 87.90 |
| Embodiment 8 | 64.31 | 82.89 |
| Comparative example 1 | 52.63 | 79.81 |
| Comparative example 2 | 52.45 | 79.54 |
Claims (7)
1. the preparation method of carbon fiber/graphite alkene/carbon nano tube/epoxy resin prepreg, it is characterised in that include successively
Following steps:
Step one: prepare Graphene
Step 2: Graphene is dissolved in dimethylformamide the uniform dispersion forming 0.1-1mg/mL, drips Carbimide.
The dimethyl formamide solution of ester in above-mentioned graphene dispersing solution and continuously stirred, mixed solution in a nitrogen atmosphere, 75-80
DEG C reaction 1h, then by dimethylformamide washing precipitation several times, adds the dimethyl formamide solution of malonaldehyde in precipitation
And one night of continuously stirred holding temperature 55 DEG C reaction, finally by centrifugal, dimethylformamide washs, and vacuum drying obtains modification
Graphene；
Step 3: preparation epoxy resin, firming agent MeTHPA are 100:60-80:8-with the mass ratio of liquid carboxy terminated nitrile rubber
Resin-the rubbery system of 12 and the quality of epoxy resin, firming agent MDA (DDM) and liquid carboxy terminated nitrile rubber
Than the resin-rubbery system for 100:30-40:8-12, it is subsequently adding multi-walled carbon nano-tubes and modified graphene, multi-wall carbon nano-tube
Managing equal with the addition quality of modified graphene, weight/mass percentage composition is 0.05wt%-1.0wt%；Then, mechanical agitation is also
After ultrasonic reaction 5-7h, add accelerator 2,4,6-tri-(dimethylamino methyl) phenol (DMP-30), and continue ultrasonic reaction one
The section time；Subsequently, place reaction liquid into de-bubbled at least 0.5h in the vacuum drying oven being preheated to 50 DEG C, obtain modified graphene/
Carbon nano tube/epoxy resin slurry；
Step 4: modified graphene/carbon nano tube/epoxy resin slurry is poured in steeping vat, and place super in steeping vat
Sonic generator, immerses in modified graphene/carbon nano tube/epoxy resin slurry by carbon fiber, and impregnation passes through one after completing
Spreading roller removes unnecessary resin adhesive liquid；
Step 5: the tow after impregnation arranges silk by the way of row's silk machine uses winding, is repeatedly wound around, forms unidirectional preimpregnation
Cloth；
Step 6: taken off by prepreg cloth, dries 7-12h under 50-70 DEG C of vacuum condition；Then at 100-120 DEG C, dry 4-6h,
Obtain carbon fiber/graphite alkene/carbon nano tube/epoxy resin prepreg.
2. according to the preparation method of a kind of carbon fiber/graphite alkene/carbon nano tube/epoxy resin prepreg described in claim 1,
It is characterized in that, prepare Graphene: weigh NaNO3Solid is dissolved in 98% concentrated sulphuric acid, is placed in ice-water bath and adds rotor not
Disconnected stirring, adds crystalline flake graphite, continuously stirred 30min, is slowly added to KMnO4, keep 0 DEG C, continue stirring 30min.Then rise
Temperature, to 35 DEG C, stirs 1h；Add deionized water and then heat to 98 DEG C, keep 15min in this temperature；Add and be preheating to 50 in advance
DEG C deionized water, add hydrogen peroxide, terminating reaction, and stirring 10min until no longer producing bubble；The hydrochloric acid of configuration 5% is molten
Liquid, joins in reaction solution, is centrifuged and is precipitated；It is precipitated to centrifugal liquid pH=7 with deionized water cyclic washing, gained is sunk
Shallow lake lyophilizing obtains graphene oxide, takes gained graphene oxide, quickly puts into holding number in the Muffle furnace being preheated to 1050 DEG C
Second expanded graphite alkene；Take a certain amount of expanded graphite alkene and add in dehydrated alcohol, ultrasonic stripping about 15h, obtain Graphene.
3. according to the preparation method of a kind of carbon fiber/graphite alkene/carbon nano tube/epoxy resin prepreg described in claim 1,
It is characterized in that, in step 2, Graphene: isocyanates: malonaldehyde use magnitude relation 100mg:0.005-0.1mol:0.05-
0.1mol。
4. according to the preparation method of a kind of carbon fiber/graphite alkene/carbon nano tube/epoxy resin prepreg described in claim 1,
It is characterized in that, ink alkene is dissolved in dimethylformamide the uniform dispersion forming 0.33mg/mL.
5. according to the preparation method of a kind of carbon fiber/graphite alkene/carbon nano tube/epoxy resin prepreg described in claim 1,
It is characterized in that, epoxy resin is E-51.
6. according to the preparation method of a kind of carbon fiber/graphite alkene/carbon nano tube/epoxy resin prepreg described in claim 1,
It is characterized in that, in step 4, control operating power at 120-170W；The control impregnation time is 8-15s, and tow tension is 160-
200 grams.
7. carbon fiber/graphite alkene/carbon nano tube/epoxy resin composite material, it is characterised in that claim 1-6 is appointed
One preparation method gained carbon fiber/graphite alkene/carbon nano tube/epoxy resin prepreg prepares laminate by hot press,
Pressure used is 5MPa, and temperature-rise period is: 90 DEG C, 1h；130 DEG C, 2h；150 DEG C, 2h, then pressurize is cooled to room temperature and obtains carbon
Fiber/graphene/carbon nano-tube/epoxy resin composite material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610339807.7A CN105968717B (en) | 2016-05-20 | 2016-05-20 | A kind of preparation of carbon fiber/graphite alkene/carbon nano tube/epoxy resin prepreg and carbon fibre composite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610339807.7A CN105968717B (en) | 2016-05-20 | 2016-05-20 | A kind of preparation of carbon fiber/graphite alkene/carbon nano tube/epoxy resin prepreg and carbon fibre composite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105968717A true CN105968717A (en) | 2016-09-28 |
| CN105968717B CN105968717B (en) | 2018-01-12 |
Family
ID=56956198
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610339807.7A Active CN105968717B (en) | 2016-05-20 | 2016-05-20 | A kind of preparation of carbon fiber/graphite alkene/carbon nano tube/epoxy resin prepreg and carbon fibre composite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105968717B (en) |
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106517178A (en) * | 2016-11-15 | 2017-03-22 | 黑龙江省科学院高技术研究院 | Preparing method of expanded graphite composite wrapped by crosslinking carbon fibers |
| CN106893157A (en) * | 2017-04-10 | 2017-06-27 | 南京工业大学 | A kind of multi-walled carbon nano-tubes enhancing heat transfer encapsulant and preparation method thereof |
| CN107057283A (en) * | 2017-01-17 | 2017-08-18 | 中国科学院理化技术研究所 | A kind of carbon fiber enhancement resin base composite material and preparation method thereof |
| CN107059403A (en) * | 2017-02-28 | 2017-08-18 | 杭州超探新材料科技有限公司 | A kind of preparation method of graphene/carbon nano-tube activeness and quietness carbon fibre composite |
| CN107674385A (en) * | 2017-10-31 | 2018-02-09 | 西南石油大学 | A kind of preparation method of toughness reinforcing drop resistance carbon fibre composite |
| CN108198937A (en) * | 2017-12-28 | 2018-06-22 | 厦门大学 | A kind of graphene/fullerene/graphene all-carbon molecular device construction method |
| CN109281157A (en) * | 2018-11-23 | 2019-01-29 | 南昌航空大学 | Graphene nanometer sheet-multi-walled carbon nanotube sizing agent modified carbon fiber method |
| CN109895469A (en) * | 2019-03-05 | 2019-06-18 | 江苏恒神股份有限公司 | A method of optimization carbon fiber in epoxy composite system interface performance |
| CN110149738A (en) * | 2019-04-22 | 2019-08-20 | 杭州电子科技大学 | It is a kind of based on graphene/ferric oxide composite material Electric radiant Heating Film and preparation method thereof |
| CN110271172A (en) * | 2019-05-22 | 2019-09-24 | 惠州龙腾运动器材有限公司 | A kind of carbon fiber bicycle part seamless pipe moulding process |
| EP3613582A1 (en) * | 2018-08-24 | 2020-02-26 | Tai Yu Arts & Development Co., Ltd. | A composite and an article comprising the same |
| KR20200023597A (en) * | 2018-08-24 | 2020-03-05 | 타이 위 아츠 ＆ 디벨롭먼트 컴퍼니 리미티드 | A composite and an article comprising the same |
| CN111113946A (en) * | 2019-12-17 | 2020-05-08 | 江苏理工学院 | Hybrid composite laminated board and preparation process thereof |
| CN111349313A (en) * | 2018-12-20 | 2020-06-30 | 帕洛阿尔托研究中心公司 | Fiber reinforced plastics reinforced with functionalized particles |
| CN111349316A (en) * | 2020-04-03 | 2020-06-30 | 广西大学 | Preparation method of inorganic fullerene resin-based composite material for containing case |
| CN111554440A (en) * | 2018-12-27 | 2020-08-18 | 广西纵览线缆集团有限公司 | High-strength aluminum alloy power transmission wire |
| CN113480833A (en) * | 2021-07-30 | 2021-10-08 | 宁波石墨烯创新中心有限公司 | Preparation method of graphene/spiral carbon fiber/epoxy resin composite material |
| CN113636854A (en) * | 2021-08-30 | 2021-11-12 | 江西信达航科新材料科技有限公司 | Carbon-carbon composite material with deposited carbon nano-tube |
| CN114426674A (en) * | 2021-12-10 | 2022-05-03 | 哈尔滨理工大学 | Preparation method and application of thermosetting resin-based toughened high-thermal-conductivity filler |
| CN114683583A (en) * | 2022-03-21 | 2022-07-01 | 中山市卡邦碳纤维材料制品有限公司 | Winding type carbon fiber pipe and processing technology thereof |
| CN114752094A (en) * | 2022-05-05 | 2022-07-15 | 富士房车（江苏）有限公司 | Preparation method of high-strength light epoxy resin composite thermal insulation material for motor home |
| CN114805882A (en) * | 2021-05-28 | 2022-07-29 | 惠州市纵胜电子材料有限公司 | High-strength antistatic 3D sheet and preparation method thereof |
| CN115141001A (en) * | 2022-04-22 | 2022-10-04 | 北京蒙京石墨新材料科技研究院有限公司 | Graphite-based electric heating material, preparation method thereof and electric heating equipment |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102304274A (en) * | 2011-06-22 | 2012-01-04 | 同济大学 | Preparation method of multidimensional hybrid composite of glass fibre/ grapheme- carbon nano tube/ epoxy resin |
| CN103552325A (en) * | 2013-10-17 | 2014-02-05 | 嘉兴学院 | Super hybrid carbon nano material modified carbon fiber/epoxy matrix composite material and preparation method thereof |
| CN103665769A (en) * | 2013-11-26 | 2014-03-26 | 上海复合材料科技有限公司 | Method for preparing nanometer-micrometer multi-scale fiber prepreg |
| CN104558525A (en) * | 2014-10-11 | 2015-04-29 | 浙江大学 | High-bending strength oxidized carbon nanomaterial/carbon fiber/epoxy resin composite material and preparation method thereof |
-
2016
- 2016-05-20 CN CN201610339807.7A patent/CN105968717B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102304274A (en) * | 2011-06-22 | 2012-01-04 | 同济大学 | Preparation method of multidimensional hybrid composite of glass fibre/ grapheme- carbon nano tube/ epoxy resin |
| CN103552325A (en) * | 2013-10-17 | 2014-02-05 | 嘉兴学院 | Super hybrid carbon nano material modified carbon fiber/epoxy matrix composite material and preparation method thereof |
| CN103665769A (en) * | 2013-11-26 | 2014-03-26 | 上海复合材料科技有限公司 | Method for preparing nanometer-micrometer multi-scale fiber prepreg |
| CN104558525A (en) * | 2014-10-11 | 2015-04-29 | 浙江大学 | High-bending strength oxidized carbon nanomaterial/carbon fiber/epoxy resin composite material and preparation method thereof |
Cited By (28)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106517178A (en) * | 2016-11-15 | 2017-03-22 | 黑龙江省科学院高技术研究院 | Preparing method of expanded graphite composite wrapped by crosslinking carbon fibers |
| CN107057283A (en) * | 2017-01-17 | 2017-08-18 | 中国科学院理化技术研究所 | A kind of carbon fiber enhancement resin base composite material and preparation method thereof |
| CN107057283B (en) * | 2017-01-17 | 2019-06-18 | 中国科学院理化技术研究所 | A kind of carbon fiber enhancement resin base composite material and preparation method thereof |
| CN107059403A (en) * | 2017-02-28 | 2017-08-18 | 杭州超探新材料科技有限公司 | A kind of preparation method of graphene/carbon nano-tube activeness and quietness carbon fibre composite |
| CN106893157A (en) * | 2017-04-10 | 2017-06-27 | 南京工业大学 | A kind of multi-walled carbon nano-tubes enhancing heat transfer encapsulant and preparation method thereof |
| CN107674385A (en) * | 2017-10-31 | 2018-02-09 | 西南石油大学 | A kind of preparation method of toughness reinforcing drop resistance carbon fibre composite |
| CN108198937B (en) * | 2017-12-28 | 2020-04-10 | 厦门大学 | Method for constructing graphene/fullerene/graphene all-carbon molecular device |
| CN108198937A (en) * | 2017-12-28 | 2018-06-22 | 厦门大学 | A kind of graphene/fullerene/graphene all-carbon molecular device construction method |
| KR20200023597A (en) * | 2018-08-24 | 2020-03-05 | 타이 위 아츠 ＆ 디벨롭먼트 컴퍼니 리미티드 | A composite and an article comprising the same |
| EP3613582A1 (en) * | 2018-08-24 | 2020-02-26 | Tai Yu Arts & Development Co., Ltd. | A composite and an article comprising the same |
| CN109281157A (en) * | 2018-11-23 | 2019-01-29 | 南昌航空大学 | Graphene nanometer sheet-multi-walled carbon nanotube sizing agent modified carbon fiber method |
| CN111349313A (en) * | 2018-12-20 | 2020-06-30 | 帕洛阿尔托研究中心公司 | Fiber reinforced plastics reinforced with functionalized particles |
| CN111554440A (en) * | 2018-12-27 | 2020-08-18 | 广西纵览线缆集团有限公司 | High-strength aluminum alloy power transmission wire |
| CN111554440B (en) * | 2018-12-27 | 2021-10-29 | 广西纵览线缆集团有限公司 | High-strength aluminum alloy power transmission wire |
| CN109895469A (en) * | 2019-03-05 | 2019-06-18 | 江苏恒神股份有限公司 | A method of optimization carbon fiber in epoxy composite system interface performance |
| CN110149738A (en) * | 2019-04-22 | 2019-08-20 | 杭州电子科技大学 | It is a kind of based on graphene/ferric oxide composite material Electric radiant Heating Film and preparation method thereof |
| CN110271172A (en) * | 2019-05-22 | 2019-09-24 | 惠州龙腾运动器材有限公司 | A kind of carbon fiber bicycle part seamless pipe moulding process |
| CN111113946A (en) * | 2019-12-17 | 2020-05-08 | 江苏理工学院 | Hybrid composite laminated board and preparation process thereof |
| CN111349316A (en) * | 2020-04-03 | 2020-06-30 | 广西大学 | Preparation method of inorganic fullerene resin-based composite material for containing case |
| CN114805882A (en) * | 2021-05-28 | 2022-07-29 | 惠州市纵胜电子材料有限公司 | High-strength antistatic 3D sheet and preparation method thereof |
| CN113480833A (en) * | 2021-07-30 | 2021-10-08 | 宁波石墨烯创新中心有限公司 | Preparation method of graphene/spiral carbon fiber/epoxy resin composite material |
| CN113480833B (en) * | 2021-07-30 | 2023-08-22 | 宁波石墨烯创新中心有限公司 | Preparation method of graphene/spiral carbon fiber/epoxy resin composite material |
| CN113636854A (en) * | 2021-08-30 | 2021-11-12 | 江西信达航科新材料科技有限公司 | Carbon-carbon composite material with deposited carbon nano-tube |
| CN114426674A (en) * | 2021-12-10 | 2022-05-03 | 哈尔滨理工大学 | Preparation method and application of thermosetting resin-based toughened high-thermal-conductivity filler |
| CN114426674B (en) * | 2021-12-10 | 2023-02-24 | 哈尔滨理工大学 | Preparation method and application of thermosetting resin-based toughened high-thermal-conductivity filler |
| CN114683583A (en) * | 2022-03-21 | 2022-07-01 | 中山市卡邦碳纤维材料制品有限公司 | Winding type carbon fiber pipe and processing technology thereof |
| CN115141001A (en) * | 2022-04-22 | 2022-10-04 | 北京蒙京石墨新材料科技研究院有限公司 | Graphite-based electric heating material, preparation method thereof and electric heating equipment |
| CN114752094A (en) * | 2022-05-05 | 2022-07-15 | 富士房车（江苏）有限公司 | Preparation method of high-strength light epoxy resin composite thermal insulation material for motor home |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105968717B (en) | 2018-01-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105968717A (en) | Preparation of carbon fiber/graphene/carbon nanotube/epoxy resin prepreg and carbon fiber composite material | |
| Yao et al. | Comparison of carbon nanotubes and graphene oxide coated carbon fiber for improving the interfacial properties of carbon fiber/epoxy composites | |
| CN105968718A (en) | Preparation method of carbon fiber/graphene/epoxy resin prepreg and carbon fiber composite material | |
| Chiou et al. | Effects of adding graphene nanoplatelets and nanocarbon aerogels to epoxy resins and their carbon fiber composites | |
| Green et al. | Multiscale fiber reinforced composites based on a carbon nanofiber/epoxy nanophased polymer matrix: synthesis, mechanical, and thermomechanical behavior | |
| Tang et al. | Interlaminar fracture toughness and CAI strength of fibre-reinforced composites with nanoparticles–A review | |
| Montazeri et al. | Mechanical properties of multi-walled carbon nanotube/epoxy composites | |
| Yeh et al. | Fabrication and mechanical properties of multi-walled carbon nanotubes/epoxy nanocomposites | |
| Njuguna et al. | Epoxy‐based fibre reinforced nanocomposites | |
| CN107057283B (en) | A kind of carbon fiber enhancement resin base composite material and preparation method thereof | |
| Pandey et al. | Carbon nanotube-based multifunctional polymer nanocomposites | |
| JP5568553B2 (en) | Carbon nanotube reinforced nanocomposite | |
| CN101418089B (en) | Method for preparing natural rubber-carbon nano tube composite material by using static electricity self-assembly | |
| Richard et al. | Reinforcement of rubbery epoxy by carbon nanofibres | |
| Wu et al. | Preparation of carbon nanotubes/waterborne polyurethane composites with the emulsion particles assisted dispersion of carbon nanotubes | |
| CN105907042B (en) | A kind of functionalized carbon nano-tube epoxy resin nano composites and preparation method thereof | |
| CN102912626B (en) | Preparation method of fiber surface sizing agent based on carbon nanotube/graphene oxide/POSS (Polysilsesquioxane) monomer | |
| CN104387671A (en) | Preparation method of PA6 (polyamide 6)/PP (polypropylene)/carbon nano tube high-performance nano composite material | |
| CN106566156B (en) | The preparation method of graphene nanobelt/PMMA fretting map nanocomposites | |
| Yesil et al. | Surfactant-modified multiscale composites for improved tensile fatigue and impact damage sensing | |
| Lin et al. | Mechanical properties of carbon nanotube fibers reinforced epoxy resin composite films prepared by wet winding | |
| CN107177165A (en) | A kind of heat-conducting type carbon nano tube/epoxy resin composite material and preparation method thereof | |
| CN109206905A (en) | A kind of graphene bismaleimide resin composite material and preparation method thereof | |
| CN109281157A (en) | Graphene nanometer sheet-multi-walled carbon nanotube sizing agent modified carbon fiber method | |
| CN103408895A (en) | Preparation method of graphene/epoxy resin composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |