CN105153639B - A kind of CNT microballoon/glass fibre cooperates with the preparation method of reinforced epoxy composite - Google Patents
A kind of CNT microballoon/glass fibre cooperates with the preparation method of reinforced epoxy composite Download PDFInfo
- Publication number
- CN105153639B CN105153639B CN201510402442.3A CN201510402442A CN105153639B CN 105153639 B CN105153639 B CN 105153639B CN 201510402442 A CN201510402442 A CN 201510402442A CN 105153639 B CN105153639 B CN 105153639B
- Authority
- CN
- China
- Prior art keywords
- cnt
- microballoon
- resin
- epoxy
- preparation
- 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.)
- Active
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/58—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising fillers only, e.g. particles, powder, beads, flakes, spheres
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
- B29K2063/00—Use of EP, i.e. epoxy resins or derivatives thereof, as moulding material
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Mechanical Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Reinforced Plastic Materials (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention discloses the preparation method that a kind of CNT microballoon glass fibre cooperates with reinforced epoxy composite, comprise the following steps：Solid epoxy is dissolved completely in organic solvent, CNT, surfactant and latent curing agent is added, CNT and epoxy resin mixed liquor is obtained after mixing, ultrasonic disperse are uniform；Mixed liquor is transferred in liquid separatnig container of the bottom with orifice or micropore, is slowly dropped into collection vessel of the lower section equipped with deionized water and dispersant；Treat that solution is dripped off, collect microballoon, and clean repeatedly, drying for standby；Microballoon is uniformly layed between glass fabric, first preheating causes microballoon melting, then using resin transfer molding process infusion epoxy resin glue, final high temperature solidification is produced.The present invention can effectively solve CNT in resin transfer molding process and be filtered and gathered problem, improve the interface binding intensity of composite, realize that the performance of composite is stable.
Description
Technical field
The invention belongs to fibre reinforced composites technical field, and in particular to a kind of CNT microballoon/glass fibre
Cooperate with the preparation method of reinforced epoxy composite.
Background technology
Glass fibre reinforced composion is with its own high intensity, high-modulus, good formability, anticorrosive and fatigue
The good characteristics such as damage, are widely used in the numerous areas such as aviation, petrochemical industry, new energy.The performance of composite is depended not only on
The performance of reinforcing fiber and matrix, and it is heavily dependent on the power of interface cohesion.Glass fibre reinforced composion
With specific strength, specific modulus is high the characteristics of, but with larger fragility, shock resistance is poor.CNT (CNTs) has
There is, and characteristic with high strength and high flexibility light compared with big L/D ratio, excellent heat conductivity, density, CNT can lead to
Cross the lifting that fibre reinforced composites performance is realized to the activeness and quietness at fiber/resin interface.Therefore CNT often by with
In galss fiber reinforced resin based composites, as study hotspot.
Currently, the major way that CNTs introduces fibre reinforced composites system is directly to mix CNTs to be scattered in resin
In, glass fibre reinforced composion is then prepared by resin transfer molding process, such as Wang Baichen [Wang Baichen, Yin Junshan,
Wang Li .RTM are molded electrical property [J] Shenyang Aerospace University journal of CNT/glass hybrid multi-dimension composite,
2013,30 (1)：61-65] it is multiple dimensioned multiple using resin transfer moulding (RTM) technique preparation CNTs/ glass fibres/epoxy hybrid
Condensation material, studies its structure and the correlation of electrical property.Zhao Yanwen etc. [Zhao Yanwen, Ye Hongjun, Zhai Yizhuo, wait CNTs/
Glass/expoxy laminate sonic vacuum instillation process and performance study [J] aeronautical material journals, 2013,33 (4)：57-63] use
Ultrasonic auxiliary vacuum instillation process prepares composite-material laminates, adds the mechanical property of composite after 0.05wt% CNTs
It is improved.Inventor's research finds that CNTs is during vacuum assisted resin instillation process (VARIM), it is easy in injecting glue
Mouthful local accumulation is caused, not only has a strong impact on the filling process of resin, and cause the skewness of CNTs in the composite,
Have a strong impact on the stability of composite property.[Elisabete F., the Reia da Costa.RTM such as Elisabete
processing and electrical performance of carbon nanotube modified epoxy/fibre
Composites [J] .Composites (Part A), 2012,43 (4)：593-602] it has also been found that being passed using vacuum assisted resin
Pass moulding process (VARTM) to prepare in composite material, the phenomenon of gum-injecting port and gum outlet CNT skewness occur.
Meanwhile, [Fan Z.H., Santarea M.H., the Advani S.G..Interlaminar shear such as Fan Z.H.
strength of glass fiber reinforced epoxy composites enhanced with multi-
walled carbon nanotubes[J].Composites Part A：Applied Science and
Manufacturing, 2008,39 (3)：540-554] research discovery, when the mass fractions of CNTs in the epoxy are less than
When 0.5%, vacuum infusion molding VARIM can be used to prepare CNTs- glass fiber/epoxy composite materials；If CNTs matter
When measuring fraction more than 0.5%, due to the filtration and through-thickness permeability reduction of fiber surface, CNTs is easily collected on
Fabric surface, substantially reduces its interlaminar improvement effect to composite, or even occurs causing to be combined because CNTs reunites
The situation of material mechanical performance reduction.Therefore, [Fan Z.H., the Santarea M.H., Advani such as Fan
S.G..Interlaminar shear strength of glass fiber reinforced epoxy composites
enhanced with multi-walled carbon nanotubes[J].Composites Part A：Applied
Science and Manufacturing, 2008,39 (3)：540-554.] it is again real using double vacuum perfusion process (DVARIM)
Now without resin penetration under positive pressure, the permeability of fabric is improved so that the CNT of high level is uniformly distributed, and is further carried
High Interlaminar shear strengths.But Chandrasekaran etc. [Chandrasekaran V.C.S., Advani S.G.,
Santare M.H..Role of processing on interlaminar shear strength enhancement of
Epoxy/glass fiber/multi-walled carbon nanotube hybrid composites [J] .Carbon,
2010,48 (13)：3692-3699.] CNT/ glasses/composite-material laminates equally are prepared for using DVARIM, the performance of laminate is simultaneously
Obvious raising does not occur.Therefore, one of key that prepared by high-performance carbon nanotube/resin composite materials is to ensure that CNTs is good
Good scattered and orientation, the enhancing at resin and interface could be so realized to greatest extent.How CNTs is improved by preparation technology
Enhancing effect also need to carry out in-depth study work.
So far it is combined there is not yet preparing glass fiber reinforcement epoxy for resin transfer molding method using CNT microballoon
The open report of material.
The content of the invention
Goal of the invention：To solve technical problem present in prior art, the present invention proposes a kind of CNT microballoon/glass
Glass fiber cooperates with the preparation method of reinforced epoxy composite, can effectively solve CNT during resin transfer molding process
Cause gather problem by fabric stop or filtering, the boundary strength of fabric reinforced composites is improved, greatly
Weaken delamination failure phenomenon, realize composite stability.
Technical scheme：To realize above-mentioned technical purpose, the present invention proposes that a kind of CNT microballoon/glass fibre collaboration increases
The preparation method of strong epoxy composite material, comprises the following steps：
(1) preparation of mixed resin solution：Solid epoxy is dissolved in water-miscible organic solvent, stirring fills it
Divide dissolving；Then CNT, surfactant and latent curing agent are added, agitated, ultrasonic disperse obtains homogeneous resin
Mixed solution；Wherein, the addition of CNT is 0.01wt%~1wt% of solid epoxy quality, surfactant
Addition be solid epoxy quality 0.01wt%~10wt%, the addition of latent curing agent is solid ring oxygen tree
10wt%~50wt% of lipid amount, it is preferable that agitated 1~2min, 30~60min of ultrasonic disperse obtain homogeneous resin mixing
Solution；
(2) preparation of CNT microballoon：Dispersant is dissolved in deionized water and obtains 0.002g/ml~0.05g/ml
Microballoon shaping dope, pour into microballoon collection vessel and stir, wherein, the consumption of dispersant is solid epoxy quality
2wt%~10wt%；Mixed resin solution in step (1) is slowly dropped into microballoon collection vessel, to mixed resin solution
After all dripping off, then the microballoon in collection vessel filtered out, cleaned repeatedly with deionized water 3~5 times, 24~48h of drying at room temperature,
CNT/epoxy microballoon is obtained, it is standby；
(3) preparation of glass fibre reinforced composion：The CNT that step (2) is obtained/epoxy microballoon is uniformly spread
Between glass fabric, first 50 DEG C~100 DEG C preheatings cause microballoon melting, are cooled to after room temperature and are transmitted again using resin
Moulding process irrigates low viscosity epoxy resin and curing agent, and CNT microballoon/glass fibre collaboration enhancing ring is obtained after solidification
O compoiste material.
Preferably, the epoxy resin that it is in solid-state at room temperature that the solid epoxy described in step (1), which is,；In step (3)
Described low viscosity epoxy resin is epoxy resin of the viscosity in 1000~3000mPas at room temperature.
Preferably, described solid epoxy is glycidol ethers, glycidol esters, glycidol amine, fat
Any one or a few mixture in ring race, epoxidation of olefins class, acid imide epoxy resin or glycolylurea epoxide resin；It is described
Low viscosity epoxy resin for glycidol ethers, glycidol esters, glycidol amine, alicyclic, epoxidation of olefins class,
Any one in acid imide epoxy resin and glycolylurea epoxide resin.
Water-miscible organic solvent described in step (1) is any one in acetone, MEK, absolute ethyl alcohol, ethylene glycol
Plant or several mixtures.
Preferably, the CNT of step (1) is to contain on the CNT of single wall, double-walled or many walls, the CNT
There is any one or a few functional group in carboxyl, amino, hydroxyl and sulfydryl.Preparation method to CNT is not limited
System, can be made by any of chemical vapour deposition technique, arc discharge method, solar energy method, template or laser evaporization method
It is standby to obtain.Contain carboxyl, amino, hydroxyl or sulfydryl on CNT, CNT in the solution scattered can be effectively improved
Property, and the curing reaction of resin system is participated in, improve the interface bond strength of resin and CNT.
Preferably, in step (1), described latent curing agent is modified imidazole class curing agent, modified dicyandiamine class is consolidated
Any one in agent and lewis acid-amine complex class curing agent.This kind of latent curing agent reactivity at room temperature
It is very low, start curing reaction under the conditions of high temperature, and it is water insoluble.
Surfactant described in step (1) is Triton X-100, polyoxyethylene sorbitan Dan Yue
Any one in cinnamic acid ester, high molecular weight alkyl ammonium salt block copolymer, the block copolymer of the affinity groups containing basic dye
Or several mixtures.
Dispersant described in step (2) is the mixed of any one in polyvinylpyrrolidone and polyethylene glycol or both
Compound.
Preferably, in step (3), glass fabric need to carry out 80 DEG C ± 10 DEG C dry 2h~4h pretreatment, wherein,
Described 100~1500g/m of glass fabric surface density2, textured structure is one-way fabric or Multi-axial stitch knitting fabric, grid
Any one in fabric, plain weave or twills.
Resin forming technique in step (3) is vacuum assisted resin instillation process, resin transfer molding (RTM) process, vacuum are auxiliary
Help resin transfer molding (RTM) process, resin dip-molding process, structural response injection molding technique, liquid resin wetting molding work
Any one in skill, Resin film infusion, vacuum bag molding moulding process.
Curing agent in step (3) is any one in ethylenediamine, triethylene tetramine, p-phenylenediamine and cyclohexanediamine.
The general principle of the present invention：CNT is dispersed in solid epoxy solution by the present invention first.Borrow
Reflect dispersion copolymerization method and emulsion polymerization, makes water insoluble oil-based liquid under high shear force stirring, is dispersed into microlayer model, and
Add after dispersant, then reduce the interfacial tension between liquid-liquid and solid-liquid, help to crush the solid after liquid liquid phase separation
Grain simultaneously prevents broken particle aggregation and keeps dispersion stable, ultimately forms stable emulsion, i.e. 10~500 μm of particle diameter distribution
Resting form carbon nanotubes epoxy microballoon.Then microballoon is uniformly layed in fiberglass surfacing, it is to avoid in filling process
The problem of CNT is stopped or filtered by fabric, CNT itself reunion can be not only reduced, strengthens CNT
With the compatibility of matrix, can also reinforcing fiber and resin matrix boundary strength, fully improve composite property.
Beneficial effect：Compared with prior art, the present invention has the following technical effect that：
(1) can effectively to solve CNT present in resin transfer molding process process fine for preparation method of the invention
The boundary strength gathered problem, effectively improve fabric reinforced composites that dimensional fabric stops or filters and cause, greatly
Weaken delamination failure phenomenon；
(2) present invention utilizes solution dispersion method, can improve the effect of impregnation of epoxy resin and CNT, effectively improve
CNT is uniformly dispersed in resin；
(3) CNT microballoon of the invention is not only good with resin matrix compatibility, effective enhanced fabrics and resin
Between interface binding intensity, additionally aid CNT being uniformly distributed in the composite, composite stress is existed
Effectively transmitted between resin and fiber, so as to improve composite overall performance；
(4) in the preparation of CNT microballoon and its glass fibre reinforced composion of the invention, stock utilization is high,
Environmental protection, and apparatus and process is simple, easily expands large-scale production.
Brief description of the drawings
Fig. 1 is the SEM figures that the embodiment of the present invention 1 prepares the distribution of CNT microballoon inner carbon nanotube；
Fig. 2 is that the embodiment of the present invention 1 prepares the stretching that CNT microballoon/glass fibre cooperates with reinforced epoxy composite
Performance map；
Fig. 3 is that the embodiment of the present invention 1 prepares the bending that CNT microballoon/glass fibre cooperates with reinforced epoxy composite
Performance map；
Fig. 4 cuts for the layer that the embodiment of the present invention 1 prepares CNT microballoon/glass fibre collaboration reinforced epoxy composite
Shear strength figure.
Embodiment
The above of the present invention is described in further detail below by way of specific embodiment.But this should not be understood
Following examples are only limitted to for present disclosure.
Embodiment 1
A kind of CNT microballoon/glass fibre cooperates with the preparation method of reinforced epoxy composite, comprises the following steps that：
(1) preparation of glass fibre：Take surface density 100g/m2One-way glass fabric, it is standby in 80 DEG C of dry 2h；
(2) preparation of resin solution：The acetone solvent that solid glycidyl ethers based epoxy resin is dissolved in, stirring treats it
Fully dissolving；In terms of the quality of solid glycidyl ethers based epoxy resin, add 0.01wt% carboxylic carbon nano-tube,
0.01wt% Triton X-100 and 15wt% modified imidazole class latent curing agent, stir 1min, ultrasound point
Dissipate 30min；Sealing preserve, it is stand-by.
(3) prepared by CNT microballoon：By 2.0% (based on the quality of solid glycidyl ethers based epoxy resin) polyethylene
Pyrrolidones dispersant is dissolved in deionized water and obtains 0.002g/ml microballoon shaping dopes, pours into the micro- of electric mixing device
In ball collection vessel, electric mixer, rotating speed 500rpm are opened；By the resin solution in step (2) from microballoon collection vessel
Side is slowly dropped into the microballoon collection vessel of lower section, titre 1.0ml/min, until resin solution is all dripped off；It will collect and hold again
Microballoon in device is filtered out, and is cleaned repeatedly 3~5 times with deionized water, drying at room temperature 24~48h, standby.
(4) preparation of glass fibre reinforced composion：The CNT microballoon of step (3) is uniformly layed in step
(1) between glass fabric, first 50 DEG C preheating 20min so that microballoon melt, cooling room temperature after again using vacuum bag molding into
Type technique, glycidyl ether type epoxy resin and ethylenediamine curing agent glue that perfusion viscosity is 1000~1400mPas,
70 DEG C of solidifications 6h, 100 DEG C of solidify afterwards 2h, so as to prepare CNT/epoxy microballoon and its glass fibre collaboration enhancing ring
O compoiste material.Fig. 1 is the SEM figures of CNT microballoon inner carbon nanotube distribution prepared by embodiment 1, as seen from Figure 1, carbon
Nanotube is evenly distributed in epoxy inner, and CNT is it is observed that very thin resin bed.Fig. 2 is prepared for the present embodiment
CNT microballoon/glass fibre cooperates with the graph of stretch performance of reinforced epoxy composite, from Figure 2 it can be seen that compared to pure glass
Fibre enhancement epoxy composite material, CNT microballoon/glass fibre cooperates with enhanced Tensile Properties of Epoxy Composites to obtain
Improve, tensile strength and modulus are respectively increased 10%, 28%.Fig. 3 prepares CNT microballoon/glass fibre association for the present embodiment
With the bending property figure of reinforced epoxy composite, as seen from Figure 3, compared to pure glass fiber reinforcement epoxy composite, carbon
Nanotube microballoon/glass fibre cooperates with enhanced epoxy composite material bending property to be improved, bending strength and modulus difference
Improve 15%, 16%.Fig. 4 prepares the layer that CNT microballoon/glass fibre cooperates with reinforced epoxy composite for the present embodiment
Shear strength figure is cut, from fig. 4, it can be seen that compared to pure glass fiber reinforcement epoxy composite, CNT microballoon/glass fibre
Cooperate with enhanced epoxy composite material layer to cut shear strength and be improved 27%, the enhancing of composite material interface bond strength is not
Merely due to the addition of CNT, can also react the dispersing uniformity of CNT from side.
Embodiment 2
A kind of CNT microballoon/glass fibre cooperates with the preparation method of reinforced epoxy composite, its with embodiment 1 not
It is that the solid epoxy described in step (2) is glycidyl ester epoxy resin, and water-miscible organic solvent is with place
MEK, described CNT is 1.0wt% (weight resin ratio), and described surfactant is 10wt% (weight resins
Than), stirring 2min, ultrasonic disperse 60min；Microballoon shaping dope is 0.04g/ml, rotating speed 3000rpm in step (3)；Step (4)
Described in low viscosity epoxy resin be viscosity be 1000~1800mPas glycidyl ester epoxy resins, resin forming work
Skill is vacuum assisted resin transfer molding technique, and curing agent is triethylene tetramine.
Embodiment 3
A kind of CNT microballoon/glass fibre cooperates with the preparation method of reinforced epoxy composite, its with embodiment 1 not
It is that surface density is 800g/m in step (1) with place2, the solid epoxy described in step (2) is glycidol amine
Epoxy resin, water-miscible organic solvent is absolute ethyl alcohol, and CNT is 0.01wt% (weight resin ratio) hydroxylatings carbon nanometer
Pipe, surfactant is 0.05wt% (weight resin ratio) polyoxyethylene 20 sorbitan monolaurate, described latency
Curing agent is 30wt% (weight resin ratio) modified dicyandiamine class curing agent；Dispersant is polyethylene glycol, rotating speed in step (3)
1000rpm, titre 2ml/min；Low viscosity epoxy resin described in step (4) is that viscosity is shunk for 1400~2000mPas
Glycerine amine epoxy resin, resin forming technique is resin dip-molding process, and curing agent is p-phenylenediamine.
Embodiment 4
A kind of CNT microballoon/glass fibre cooperates with the preparation method of reinforced epoxy composite, its with embodiment 1 not
It is that surface density is 800g/m in step (1) with place2Multi-axial fabric, the solid epoxy described in step (2) is fat
Ring same clan epoxy resin, water-miscible organic solvent is absolute ethyl alcohol, and CNT is 0.1wt% (weight resin ratio) hydroxylating carbon
Nanotube, surfactant is 10wt% (weight resin ratio) polyoxyethylene 20 sorbitan monolaurate, and described is latent
Property curing agent is 30wt% (weight resin ratio) modified dicyandiamine class curing agent；Dispersant is polyethylene glycol, microballoon in step (3)
Shaping dope is 0.01g/ml, rotating speed 1500rpm；Low viscosity epoxy resin described in step (4) is viscosity for 1500~
The alicyclic based epoxy resins of 2000mPas, resin forming technique is structural response injection molding technique, and curing agent is to benzene two
Amine.
Embodiment 5
A kind of CNT microballoon/glass fibre cooperates with the preparation method of reinforced epoxy composite, its with embodiment 1 not
It is that surface density is 1500g/m in step (1) with place2Grid fabric, the solid epoxy described in step (2) is ring
Oxyalkylene based epoxy resin, water-miscible organic solvent is ethylene glycol, and CNT is 0.1wt% (weight resin ratio) amination
CNT, surfactant is 5wt% (weight resin ratio) molecular weight alkyl radical ammonium salt block copolymer Bs YK-9076, described
Latent curing agent is 10wt% (weight resin ratio) lewis acid-amine complex class curing agent；Dispersant is poly- in step (3)
Vinylpyrrolidone and polyethylene glycol mixture, microballoon shaping dope are 0.02g/ml, and rotating speed is 1500rpm；Described in step (4)
Low viscosity epoxy resin be viscosity be 2000~2500mPas epoxidation of olefins based epoxy resins, curing agent be hexamethylene two
Amine.
Embodiment 6
A kind of CNT microballoon/glass fibre cooperates with the preparation method of reinforced epoxy composite, its with embodiment 1 not
It is that surface density is 1500g/m in step (1) with place2Plain cloth, the solid epoxy described in step (2) is acyl
Imide-epoxy resin, water-miscible organic solvent is ethylene glycol, and CNT is 1wt% (weight resin ratio) aminations carbon nanometer
Pipe, surfactant for 10wt% (weight resin ratio) affinity groups containing basic dye block copolymer B YK-2150, it is described
Latent curing agent be 10wt% (weight resin ratio) lewis acid-amine complex class curing agent；Dispersant is in step (3)
Polyvinylpyrrolidone or polyethylene glycol mixture, microballoon shaping dope are 0.05g/ml, rotating speed 3000rpm；Described in step (4)
Low viscosity epoxy resin be viscosity be 2000~3000mPas acid imide epoxy resin, resin transfer molding process is liquid
Resin wetted moulding technology, curing agent is cyclohexanediamine.
Claims (9)
1. a kind of CNT microballoon/glass fibre cooperates with the preparation method of reinforced epoxy composite, it is characterised in that including
Following steps：
（1）The preparation of mixed resin solution：Solid epoxy is dissolved in water-miscible organic solvent, stirring makes it fully molten
Solution；Then CNT, surfactant and latent curing agent are added, agitated, ultrasonic disperse obtains mixed resin solution；
Wherein, the addition of CNT is 0.01wt%~1wt% of solid epoxy quality, and the addition of surfactant is solid
0.01wt%~10wt% of body epoxy resin quality, the addition of latent curing agent is the 10wt% of solid epoxy quality
~50wt%；
（2）The preparation of CNT microballoon：Dispersant is dissolved in and obtains the g/ml's of 0.002 g/ml~0.05 in deionized water
Microballoon shaping dope, pours into microballoon collection vessel and stirs；Wherein, the consumption of dispersant for solid epoxy quality 2wt%~
10wt%；By step（1）In mixed resin solution be slowly dropped into microballoon collection vessel, all dripped off to mixed resin solution
Afterwards, then by the microballoon in collection vessel filter out, cleaned repeatedly with deionized water 3~5 times, 24~48h of drying at room temperature obtains carbon
Nanotube/epoxy microballoon, it is standby；
（3）The preparation of glass fibre reinforced composion：By step（2）Obtained CNT/epoxy microballoon is uniformly layed in
Between glass fabric, first 50 DEG C~100 DEG C preheatings cause microballoon melting, are cooled to after room temperature and use resin transfer molding again
Technique irrigates low viscosity epoxy resin and curing agent mixed liquor, and CNT microballoon/glass fibre collaboration enhancing is obtained after solidification
Epoxy composite material；Wherein, step（1）Described in solid epoxy be at room temperature be in solid-state epoxy resin；Step（3）
Described in low viscosity epoxy resin be epoxy resin of the viscosity in 1000~3000mPa s at room temperature.
2. CNT microballoon according to claim 1/glass fibre cooperates with the preparation method of reinforced epoxy composite,
Characterized in that, described solid epoxy be glycidol ethers, glycidol esters, glycidol amine, it is alicyclic,
Any one or a few mixture in epoxidation of olefins class, acid imide epoxy resin or glycolylurea epoxide resin；Described is low
Viscosity epoxy is glycidol ethers, glycidol esters, glycidol amine, alicyclic, epoxidation of olefins class, acyl Asia
Any one in amine epoxy resin and glycolylurea epoxide resin.
3. CNT microballoon according to claim 1/glass fibre cooperates with the preparation method of reinforced epoxy composite,
Characterized in that, step（1）Described in water-miscible organic solvent be any in acetone, MEK, absolute ethyl alcohol, ethylene glycol
One or more of mixtures.
4. a kind of CNT microballoon according to claim 1/glass fibre cooperates with the preparation of reinforced epoxy composite
Method, it is characterised in that step（1）CNT be single wall, double-walled or many walls CNT, contain on the CNT
There is any one or a few functional group in carboxyl, amino, hydroxyl and sulfydryl.
5. CNT microballoon according to claim 1/glass fibre cooperates with the preparation method of reinforced epoxy composite,
Characterized in that, step（1）In, described latent curing agent is modified imidazole class curing agent, modified dicyandiamine class curing agent
With any one in lewis acid-amine complex class curing agent.
6. CNT microballoon according to claim 1/glass fibre cooperates with the preparation method of reinforced epoxy composite,
Characterized in that, step（1）Described in surfactant be Triton X-100, polyoxyethylene sorbitan list
It is any one in laurate, high molecular weight alkyl ammonium salt block copolymer, the block copolymer of the affinity groups containing basic dye
Plant or several mixtures.
7. CNT microballoon/glass fibre according to claim 1 cooperates with the preparation side of reinforced epoxy composite
Method, it is characterised in that step（2）Described in dispersant be polyvinylpyrrolidone and polyethylene glycol in any one or two
The mixture of person.
8. CNT microballoon according to claim 1/glass fibre cooperates with the preparation method of reinforced epoxy composite,
Characterized in that, step（3）In resin transfer molding process be vacuum assisted resin instillation process, resin transfer moulding work
Skill, vacuum assisted resin transfer molding technique, resin dip-molding process, structural response injection molding technique, liquid resin profit
Any one in wet moulding technology, Resin film infusion, vacuum bag molding moulding process.
9. CNT microballoon according to claim 1/glass fibre cooperates with the preparation method of reinforced epoxy composite,
Characterized in that, step（3）In curing agent be ethylenediamine, triethylene tetramine, p-phenylenediamine and cyclohexanediamine in it is any one
Kind.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510402442.3A CN105153639B (en) | 2015-07-09 | 2015-07-09 | A kind of CNT microballoon/glass fibre cooperates with the preparation method of reinforced epoxy composite |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510402442.3A CN105153639B (en) | 2015-07-09 | 2015-07-09 | A kind of CNT microballoon/glass fibre cooperates with the preparation method of reinforced epoxy composite |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105153639A CN105153639A (en) | 2015-12-16 |
| CN105153639B true CN105153639B (en) | 2017-07-18 |
Family
ID=54794706
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510402442.3A Active CN105153639B (en) | 2015-07-09 | 2015-07-09 | A kind of CNT microballoon/glass fibre cooperates with the preparation method of reinforced epoxy composite |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105153639B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105648775B (en) * | 2015-12-29 | 2018-09-07 | 哈尔滨工业大学 | A kind of preparation method of carbon fibre reinforced composite |
| CN110655679B (en) * | 2019-10-14 | 2022-02-11 | 江西铜业技术研究院有限公司 | Carbon nanotube pre-dispersion for modified epoxy resin and preparation method thereof |
| WO2021092787A1 (en) * | 2019-11-13 | 2021-05-20 | 远景能源有限公司 | Method and apparatus for manufacturing carbon-nanotube-modified fiber reinforced material |
| CN112980026A (en) * | 2021-03-09 | 2021-06-18 | 山东非金属材料研究所 | Preparation method of carbon nanotube modified fiber reinforced thermosetting resin-based prepreg |
| CN114381092A (en) * | 2021-07-30 | 2022-04-22 | 江苏博泓新材料科技有限公司 | High-temperature thickening vinyl resin and preparation method thereof |
| CN118398315B (en) * | 2024-06-26 | 2024-09-20 | 西安天工电气有限公司 | Layered wound composite coat metal oxide lightning protection core and preparation process thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102712764A (en) * | 2009-11-18 | 2012-10-03 | 拜耳材料科技股份有限公司 | Method for producing composite materials based on polymers and carbon nanotubes (CNTS), and composite materials produced in this manner and the use thereof |
| CN104194007A (en) * | 2014-09-28 | 2014-12-10 | 中国科学院理化技术研究所 | Preparation method of polymer-based micro/nano filler filled modified composite premix particles |
| CN104327454A (en) * | 2014-10-11 | 2015-02-04 | 沈阳航空航天大学 | Preparation method of carbon nanotube/continuous fiber hybrid reinforced composite material |
| CN104525070A (en) * | 2015-01-04 | 2015-04-22 | 黑龙江大学 | Method for manufacturing carbon nano tube micro beads |
-
2015
- 2015-07-09 CN CN201510402442.3A patent/CN105153639B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102712764A (en) * | 2009-11-18 | 2012-10-03 | 拜耳材料科技股份有限公司 | Method for producing composite materials based on polymers and carbon nanotubes (CNTS), and composite materials produced in this manner and the use thereof |
| CN104194007A (en) * | 2014-09-28 | 2014-12-10 | 中国科学院理化技术研究所 | Preparation method of polymer-based micro/nano filler filled modified composite premix particles |
| CN104327454A (en) * | 2014-10-11 | 2015-02-04 | 沈阳航空航天大学 | Preparation method of carbon nanotube/continuous fiber hybrid reinforced composite material |
| CN104525070A (en) * | 2015-01-04 | 2015-04-22 | 黑龙江大学 | Method for manufacturing carbon nano tube micro beads |
Non-Patent Citations (1)
| Title |
|---|
| 基于碳纳米管复合纤维预制体的复合材料结构和性能;王柏臣等;《固体火箭技术》;20140831;第37卷(第4期);第578-582页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105153639A (en) | 2015-12-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105153639B (en) | A kind of CNT microballoon/glass fibre cooperates with the preparation method of reinforced epoxy composite | |
| Jiang et al. | Electrospun nanofiber reinforced composites: A review | |
| Zhang et al. | Preparation of aramid nanofiber and its application in polymer reinforcement: A review | |
| Li et al. | Synchronous effects of multiscale reinforced and toughened CFRP composites by MWNTs-EP/PSF hybrid nanofibers with preferred orientation | |
| CN103665769B (en) | The preparation method of the multiple dimensioned fiber prepreg material of nano-micrometre | |
| JP5704198B2 (en) | Method for producing cellulose nanofiber-containing epoxy resin composition, reinforced matrix resin, and fiber-reinforced resin composite | |
| CN107057283B (en) | Carbon fiber reinforced resin matrix composite material and preparation method thereof | |
| Chen et al. | Electrospinning fabrication of high strength and toughness polyimide nanofiber membranes containing multiwalled carbon nanotubes | |
| KR101445169B1 (en) | Prepreg, preform, molded product, and method for manufacturing prepreg | |
| CN103317734B (en) | Method for preparing radar wave-absorbing composite material based on carbon nanometer film | |
| CN107674385B (en) | A kind of preparation method of toughening drop resistance carbon fibre composite | |
| CN106633391B (en) | A kind of abductive approach of polypropylene/glass fiber interface scorching structure | |
| CN103938366A (en) | Method for preparing graphene oxide and polyving akohol composite membrane through electrostatic spinning | |
| CN104327454B (en) | A kind of preparation method of CNT/continuous fiber hybrid buildup composite | |
| Luo et al. | Investigation of properties of nano-silica modified epoxy resin films and composites using RFI technology | |
| CN104558525A (en) | High-bending strength oxidized carbon nanomaterial/carbon fiber/epoxy resin composite material and preparation method thereof | |
| CN104448239A (en) | High-strength epoxy resin composite material and preparation method thereof | |
| CN111057346B (en) | Carbon fiber reinforced PEEK unidirectional tape and preparation method thereof | |
| CN105060268A (en) | Preparation method of CNT (carbon nanotube) microspheres | |
| Jiménez-Suárez et al. | Dispersion of carbon nanofibres in a low viscosity resin by calendering process to manufacture multiscale composites by VARIM | |
| CN105713234B (en) | A kind of preparation method and application of carbon fibre reinforced high-molecular based composites | |
| CN106245138A (en) | A kind of preparation method of high recovery stress shape memory complex fiber material | |
| CN108676358B (en) | method for preparing polyphenylene sulfide thermoplastic prepreg with improved permeability | |
| CN105690802A (en) | Preparation method and application of carbon-fiber-reinforced macromolecule-based composite | |
| CN108943767B (en) | Toughening modification method of 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 |