CN107698739A - The preparation method of the silane coupler modified epoxy resin composite materials of CNTs/CFDSF/AG 80 - Google Patents
The preparation method of the silane coupler modified epoxy resin composite materials of CNTs/CFDSF/AG 80 Download PDFInfo
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- CN107698739A CN107698739A CN201710869881.4A CN201710869881A CN107698739A CN 107698739 A CN107698739 A CN 107698739A CN 201710869881 A CN201710869881 A CN 201710869881A CN 107698739 A CN107698739 A CN 107698739A
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- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
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Abstract
The present invention relates to a kind of preparation method of the silane coupler modified epoxy resin composite materials of CNTs/CFDSF/AG 80,This method mainly includes the first step being acidified to CNT (CNTs) using the mixed acid solution of concentrated nitric acid and the concentrated sulfuric acid,Obtained O CNTs after acidification are passed through into silane coupler modified second step,The third step of surface clean and surface modification treatment is carried out to carbon fiber double-layer partition fabric (CFDSF) and the modified epoxy-resin systems solution of CNTs/AG 80 will be prepared CFDSF is poured and the four steps of heat cure,It has been prepared by above-mentioned preparation process of the invention and its specific technological parameter with excellent conductive performance,Thermodynamic property and silane coupler modified CNTs/CFDSF/AG 80 epoxy resin composite material few to conductive material dosage,Its modified carbon nano-tube is uniformly distributed in the base,The composite has good conductive stability,Electronics can be widely used in,Electrostatic protection,Electromagnetic shielding,The fields such as microwave absorption.
Description
Technical field
The present invention relates to field of compound material, and in particular to (carbon fiber is double by a kind of silane coupler modified CNTs/CFDSF
Layer space fabric)/AG-80 epoxy resin composite materials and preparation method thereof.
Background technology
With making rapid progress for electronics technology industry, to the demand of the functional composite material with excellent conductive performance
It is increasing.Due to conducing composite material have light weight, non-corroding, good stability of the dimension, electrical conductivity it is interior in a big way can
The characteristics of tune, while be also easy to be processed into various complicated shapes and be easy to mass industrialized production, thus it prevents in electrostatic
The field such as shield, electromagnetic shielding, microwave absorption is widely used.Conducing composite material common at present is generally using macromolecule as its base
Body, while the conductive materials such as carbon-based material, metal packing are added, it is compound by method progress physically or chemically, both had
There is the heterogeneous composite material that certain electric conductivity has excellent mechanical performances again.
Carbon-based material mainly includes carbon black (carbon black abbreviation CB), graphite, carbon fiber (carbon fiber letters
Claim CF), CNT (carbon nanotubes abbreviation CNTs) etc., they are the important of conductive filler in conducing composite material
Part.Due to the polymer composites easy-formation of carbon-based material filling, do not limited and corrosion-resistant by compact dimensions, can be with
Use under some specific environments, thus be taken seriously in more and more fields.
CNT is in light weight as monodimension nanometer material, and hexagonal structure connection is perfect, is referred to as " ultimate " fiber,
With many abnormal mechanics, electricity and chemical properties, CNTs carries out division by the structure of each aspect can be divided into not helical
With the class of screw type two, the different number of plies differences mutually formed according to graphite flake, CNTs be divided into again single-walled carbon nanotube with it is more
The class of wall carbon nano tube two.CNTs excellent in mechanical performance, its intensity is about hundred times of steel, and its density just corresponds to six points of steel
One of, shear strength is about 500MPa between each layers of CNTs, significantly larger than most of CF enhancings composites；On electric conductivity
Can, CNTs can not only possess the excellent electric conductivity of metal material, can also fully show the electrical characteristic of semiconductor, and
And the performance of superconduction is shown at a lower temperature, and CNTs critical supercurrent is bigger；On thermal property, CNTs
Thermal property not only with form it graphite flake it is relevant, also relevant with size with its unique structure, the group such as CNTs and graphite
It is identical into composition, all it is extremely excellent heat conductor, when CNTs makees Heat Conduction Material, its heat transfer rate can reach 1000m/s.
Although CNTs has special mechanics, electricity and chemical property, there is great application value, really to realize
CNTs maximum value, there are many crucial technologies to need to overcome, what is stood in the breach is CNTs dispersing characteristic, and this is to realize
The key of CNTs values, needs to be modified CNTs for this, mainly have to CNTs method of modifying at present physical modification method with
Chemical modification method.Physical modification method mainly changes CNTs surface-active by the physical action such as adsorbing, applying and coat
Group, so as to improve its associativity with matrix, wherein comparing typically polymer wrapped method and surfactant-modified
Method, CNTs C atoms are because of SP2For hydridization so as to form highly delocalized pi-electron, they can be with equally containing π electricity
The different polymer of son are combined by π-π non-covalent bonds, so as to obtain the CNTs with some specific functions；Chemical modification
Method mainly using the means such as grafting, oxidation is introduced directly in CNTs side wall micromolecular compound or active functional group group (such as-
COOH, OH and-NH2) etc., its activity is improved, so as to increase its dispersiveness and compatibility in solution and polymer.
At present, the domestic and international present Research of carbon nano tube/epoxy resin composite material is as follows：
Florian etc. is in " Influence of different carbon nanotubes on the mechanical
properties of epoxy matrix composites-A comparative study.Composites Science
Influence of the CNTs content to epoxy matrix composite electric conductivity and conductivity of heat has been probed into and Technology ".It is real
Analysis shows are tested, when system all reaches critical content, content needed for CNTs is far less than CB, and the electrical conductivity meeting of composite
Increase with the increase of CNTs contents.
Via Michael D. et al. are in " Electrical conductivity modeling of carbon
black/polycarbonate,carbon nanotube/polycarbonate,and exfoliated Graphite
Ground in nanoplatelet/polycarbonate composites.Journal ofApplied Polymer Science "
Study carefully and CNTs, CB conductive filler different with the classes of GNP tri- have been separately added into polycarbonate matrix, and to corresponding composite
Electric conductivity is deeply probed into.Research finds that CNTs threshold value shows to add in PC for 1.2vol% and result of study
The electric conductivity of its composite of CNTs is best.
Wei little Xin have studied in " research of surface-modified carbon nanotubes/epoxy resin composite material mechanical property " paper
Influence of the modified CNTs content to epoxy matrix composite mechanical property.As a result show, by modified CNTs, it is scattered
Property is better than unmodified CNTs, meanwhile, with the gradual increase of CNTs contents, the mechanics of CNTs/ epoxy resin composite materials
Performance first increases and subtracted afterwards, and ultimate tensile strength is 67.3MPa, absolutely prove modified CNTs have to the performance of matrix material compared with
Good lifting.
Zeng Qin has probed into containing for CNTs in " preparation of carbon nano tube/epoxy resin composite material and performance study " paper
Measure the influence to epoxy resin thermal property.Result of study shows, composite wood can be effectively facilitated with the increase of CNTs contents
The curing reaction of material, and its thermal property can also be effectively improved, show that CNTs has good heat resistance.
Zhang Qiuju have studied fiber in " electricity of fiber-reinforced modified epoxy systems and mechanical property research " paper and increase
The electricity and mechanical property of strong modified epoxy system, have been directed to a kind of preparation of carbon fiber/epoxy resin composite material, its
It is to be added in AG-80 epoxy resin-bases to form composite as reinforcement after carbon fiber is made into space fabric processing,
Although the composite improves its thermodynamic property, electric conductivity and its stability are still not being met.
Chinese patent application (201010221872.2) discloses a kind of multi-walled carbon nanotube (MWNTs) hybridized CF/EP layers
The preparation method of plywood composite, the preparation method of the composite, which includes MWNTs dispersant being ultrasonically treated, to be obtained
Even scattered MWNTs dispersion liquids, recycle sprayer that MWNTs homogeneous dispersions are sprayed on carbon fibre fabric, at drying
Hot-forming with epoxy resin again after reason, this application enters MWNTs in CF/EP composites, improves carbon fibre fabric
Surface property, improve the mechanical property of composite, but the electric conductivity deficiency of the material.
Research understands CNTs content and the difference of modification mode, the influence to composite system performance more than
Have very big difference.Although CNTs addition can effectively improve the electric conductivity of composite system, as CNTs contents increase
After being added to a certain section, downward trend can be presented on the contrary for its mechanical property, and overall mechanical properties are not excellent, it is therefore desirable to
Processing is modified to conductive filler or needs to probe into synergy of the multicomponent conductive filler to composite, has been solved multiple
Close conductive material developing above-mentioned bottleneck problem at present.
The content of the invention
The present invention is filled out by the modification to conductive filler and to multicomponent precisely in order to overcome above-mentioned technical problem
The mixing of material is studied and then provided to improve the method for composite system electric property, mechanical property, thermal property etc.
It is a kind of that there is excellent conductive performance, thermodynamic property and the silane coupler modified CNTs/CFDSF/ few to conductive material dosage
AG-80 epoxy resin composite materials and preparation method thereof.For this following technical scheme provided by the present invention：
A kind of preparation method of silane coupler modified CNTs/CFDSF/AG-80 epoxy resin composite materials, its feature exist
In the preparation method specifically includes following steps：
(1) CNTs is acidified using the mixed acid solution of concentrated nitric acid and the concentrated sulfuric acid, 2~5g CNTs are placed in 250~
In 500ml concentrated nitric acid and the mixed acid solution of the concentrated sulfuric acid, wherein the volume ratio of concentrated nitric acid and the concentrated sulfuric acid is 3:1~4:1, room temperature surpasses
Distilled water is added in mixed solution to be diluted, filtered with filter membrane, appropriate distillation is continuously added after filtering after 3~4h of sonication
Water dilutes, and stands, takes supernatant liquor to outwell, and filters, and repeats operation above for several times, until supernatant liquor pH value is 7 or so, will filter
Membrane filtration goes out CNTs, and 0.5~1h, the CNT O-CNTs being acidified are ground after placing oven drying；
(2) silane coupler modified CNTs preparation, the sufficient O- of grinding that a certain amount of step (1) obtains is weighed
CNTs, appropriate KH550 and DCC are added, being ultrasonically treated makes it well mixed for 2~3 hours, and 4~6h of stirring makes it fully react, will
The appropriate washes of absolute alcohol of the mixed solution that reaction obtains, to remove unreacted KH550 and DCC, filtering, dry, grind
0.5~1h is ground, so as to obtain silane coupler modified CNT Si-CNTs；
(3) carbon fiber double-layer partition fabric (CFDSF) is handled, the carbon fiber weaved, cut in advance is double-deck
Space fabric carries out surface clean and surface modification treatment, concrete technology are：At room temperature, by between the carbon fiber bilayer cut
It is placed in every fabric in ultrasonic cleaning solution and carries out washing 30~50min after 1~2h of immersion, is then taken out in 95~110 DEG C of conditions
Lower drying, a certain amount of mass percent containing absolute ethyl alcohol for being dissolved in water is coated after drying on double-layer partition fabric as 1.5
~3wt% Silane coupling agent KH550 solution, 24h~36h is placed at room temperature, so that ethanol volatilization is complete, seal up for safekeeping stand-by；
(4) prepare modified CNTs/AG-80 epoxy-resin systems solution to pour CFDSF and heat cure, by AG-80
Epoxy resin, hexahydrophthalic anhydride curing agent, 2,4,6- bis aminomethyl phenol accelerator, acetone and absolute ethyl alcohol dilution
Agent, it is respectively placed in 38~45 DEG C of baking oven and preheats 1~2 hour, weigh 0.3~2.7g and account for 0.5~4.5wt% of epoxy resin simultaneously
The modified carbon nano-tube Si-CNTs sufficiently after the step (2) processing is ground, is placed it in ultrasonic in proper amount of acetone solution
Ripple handle 0.5~1h after, poured into by proportioning in epoxy resin, 35~45 DEG C stir 4~6h after, be ultrasonically treated 2~3h after
80~90 DEG C vacuumize 2~3h, after then pouring into the curing agent, accelerator, diluent successively, by mixed solution 40~50
DEG C 0.5~1h is sufficiently stirred, 65~75 DEG C vacuumize 0.5~1h, obtain being modified CNTs/AG-80 epoxy-resin systems solution；With
Place the carbon fiber double-layer partition fabric after the step (3) processing in a mold afterwards, coat appropriate methyl-silicone oil, pour above-mentioned
Whole mould is vacuumized into 1~2h after modified CNTs/AG-80 epoxy-resin systems solution, 36~48h is stood, then certain
Heat cure is carried out under temperature time protocols, it is compound to obtain silane coupler modified CNTs/CFDSF/AG-80 epoxy resin through cooling
Material.
Preferably, the sufficient O-CNTs of grinding that 1~3g obtains through the step (1) is weighed in the step (2), is added
Appropriate 500~1000ml mass fractions are 3wt%~5wt% KH550 and 0.2~0.3g DCC, are ultrasonically treated 2~3 hours
Make it well mixed, 4~6h of stirring makes it fully react.
Preferably, ultrasonic cleaning solution described in the step (3) be 10~30wt% ethanol solutions and 20~
40wt% acetone solns press volume 1:1~1:1.5 mixed liquor.
Preferably, in the step (4), the AG-80 epoxy resin, curing agent, the ratio of diluent for 45~
50wt%：40~45wt%:5~15wt%, the volume ratio of absolute ethyl alcohol and acetone is 1 in the diluent:1~1:1.5.
Preferably, the heat cure in the step (4) is the solidification work according to pure CNTs/CFDSF/AG-80 composites
80 DEG C/0.5h → 110 DEG C of skill/0.5h → 120 DEG C/4h → 150 DEG C/4h carries out heat cure.
Preferably, it is that the carbon fiber double-layer partition fabric is that upper and lower surface layer is that plain weave is knitted in the step (3)
Thing.
Preferably, the modified carbon nano-tube in the step (4) accounts for 2.5~4.5wt% of epoxy resin.
The advantageous effects that the present invention is obtained：
1. the present invention is modified using silane coupler to CNT, set by its specific modified technique and parameter
Count and select to make modified carbon nano-tube first with AG-80 epoxy resin certain as matrix using carbon fiber double-layer partition fabric
Technique and Parameter Conditions under be mixed to form modified CNTs/AG-80 epoxy-resin systems solution, finally by modification CNTs/AG-
80 epoxy-resin systems solution are poured to being pre-placed in the mould of carbon fiber double-layer partition fabric by heat curing process system
It is standby to have obtained with excellent conductive performance, thermodynamic property and the silane coupler modified CNTs/ few to conductive material dosage
CFDSF/AG-80 epoxy resin composite materials, use the modification CNTs techniques of the present invention and made with carbon fiber double-layer partition fabric
For matrix, its CNT can be uniformly distributed in the base, so as to ensure that the stability of its electric conductivity；
2. the present invention to carbon fiber double-layer partition fabric when cleaning using ultrasonic cleaning process and by cleaning fluid
Volume 1 is pressed using 10~30wt% ethanol solutions and 20~40wt% acetone solns:1~1:1.5 mixed liquor, can be fast
Greasy dirt that the removings carbon fiber surface of speed is adhered during weaving or touch, impurity etc., are modified with being more beneficial for its surface
Processing；
3. the present invention is it is determined that pass through the starting temperature to pure CNTs/CFDSF/AG-80 systems in the technical process of heat cure
Degree, summit temperature and peak valley temperature make linear regression analysis, are obtained according to the linear regression analysis of different temperatures：It is final to determine to be somebody's turn to do
The curing process of system is：80 DEG C/0.5h → 110 DEG C/0.5h → 120 DEG C/4h → 150 DEG C/4h carries out heat cure, is improving heat
Without the characteristic of influence composite while curing efficiency.
Brief description of the drawings
Fig. 1 is that Si-CNTs/CFDSF/AG-80 composites of the present invention prepare schematic diagram；
Fig. 2 a are the scanning electron microscope (SEM) photograph in Si-CNTs/CFDSF/AG-80 composite impacts section dimple area of the present invention；
Fig. 2 b are the scanning electron microscope (SEM) photograph in Si-CNTs/CFDSF/AG-80 composite impacts section river area of the present invention；
Fig. 3 a are Si-CNTs/CFDSF/AG-80 composites storage modulus E ' of the present invention dynamic analysis figure；
Fig. 3 b are Si-CNTs/CFDSF/AG-80 composites loss modulus E " of the present invention dynamic analysis figure；
Fig. 4 a are the thermal weight loss TG curve maps of Si-CNTs/CFDSF/AG-80 composites of the present invention；
Fig. 4 b are the DTG curve maps of Si-CNTs/CFDSF/AG-80 composites of the present invention；
Fig. 5 shows shadow of the modified CNTs contents of the present invention to modified CNTs/CFDSF/AG-80 composite electric properties
Ring.
Embodiment
Technical scheme is described in detail below by embodiment, it is only the specific of the present invention
Ground embodiment or preferable embodiment, are not thereby limited the scope of the invention.
Embodiment 1
Modification to CNT (CNTs), present inventor have studied to be modified using silane coupler
Handle and be modified processing only with acidifying, present invention protection uses silane coupler modified CNTs/CFDSF/AG-80 epoxies
The preparation method of resin composite materials；
A kind of preparation method for preparing silane coupler modified CNTs/CFDSF/AG-80 epoxy resin composite materials, mainly
Comprise the following steps：
1. pair CNT (CNTs) is modified processing using silane coupler
1.1) processing is modified using silane coupler to CNT (CNTs), acidification is carried out to it first：
CNTs is acidified using the mixed acid solution of concentrated nitric acid and the concentrated sulfuric acid, 2g CNTs are placed in 250ml concentrated nitric acid
In the mixed acid solution of the concentrated sulfuric acid, wherein the volume ratio of concentrated nitric acid and the concentrated sulfuric acid is 3:It is molten in mixing after 1, room temperature supersound process 3h
Distilled water is added in liquid to be diluted, and is filtered with filter membrane, appropriate distilled water diluting is continuously added after filtering, stood, take upper strata clear
Liquid is outwelled, and is filtered, and repeats operation above for several times, until supernatant liquor pH value is 7 or so, membrane filtration is gone out into CNTs, places baking
Case grinds 0.5h after drying, the CNT O-CNTs being acidified；
1.2) silane coupler modified CNTs preparation
The sufficient O-CNTs of the grinding obtained in a certain amount of step 1.1) is weighed, adds appropriate KH550 and DCC, ultrasound
Processing makes it well mixed for 2 hours, and stirring 4h makes it fully react, and the mixed solution that reaction is obtained is clear with appropriate absolute ethyl alcohol
Wash, to remove unreacted KH550 and DCC, filtering, dry, 0.5h is ground, so as to which the carbon for obtaining silane coupler modified is received
Mitron Si-CNTs；
2. a pair carbon fiber double-layer partition fabric (CFDSF) is handled
The characteristics of Woven Distance Fabric maximum is that a determining deviation can be formed between two parallel flat fabrics, the present invention
Using woven double-layer partition fabric, connected between fabric upper layer 1 and cutting optimal 2 as shown in Figure 1 by binder yarn 3, by modification
CNTs/AG-80 epoxy-resin systems solution pours the composite for being cured to and the present invention being obtained in the space fabric；In the present invention
In due to using the specification of mould 1 as 14cm × 14.5cm, it requires specification that all CFDSF fabrics cut for 14cm ×
14.5cm；
The carbon fiber double-layer partition fabric weaved, cut in advance is subjected to surface clean and surface modification treatment, that is, existed
At room temperature, the carbon fiber double-layer partition fabric cut is placed in ultrasonic cleaning solution after carrying out immersion 1h and washs 30min, so
After take out and dried under the conditions of 95 DEG C, coated after drying on double-layer partition fabric it is a certain amount of be dissolved in water containing absolute ethyl alcohol
Mass percent is 1.5wt% Silane coupling agent KH550 solution, places 24h at room temperature, so that ethanol volatilization is complete, is sealed up for safekeeping
It is stand-by；
3. CFDSF is poured preparation modified CNTs/AG-80 epoxy-resin systems solution and heat cure
By AG-80 epoxy resin, hexahydrophthalic anhydride curing agent, 2,4,6- bis aminomethyl phenol accelerator, third
Ketone and absolute ethyl alcohol diluent, it is respectively placed in 38 DEG C of baking oven and preheats 1 hour, weigh 0.3g and account for epoxy resin 0.5wt% simultaneously
Grinding sufficiently handles modified Si-CNTs through step 1.2), places it in ultrasonication 0.5h in proper amount of acetone solution
Afterwards, poured into by proportioning in epoxy resin, after 35 DEG C are stirred 6h, be ultrasonically treated after 2h and vacuumize 2h at 80 DEG C, then fall successively
After entering the curing agent, accelerator, diluent, mixed solution is sufficiently stirred 0.5h at 40 DEG C, 65 DEG C vacuumize 0.5h, obtain
Modified CNTs/AG-80 epoxy-resin systems solution；Then place in a mold between the carbon fiber bilayer after the step 2 processing
Every fabric, appropriate methyl-silicone oil is coated, takes out whole mould after pouring above-mentioned modified CNTs/AG-80 epoxy-resin systems solution
Vacuum 1h, 36h is stood, heat cure is then carried out under certain temperature time conditions, obtained through cooling silane coupler modified
CNTs/CFDSF/AG-80 epoxy resin composite materials.
Embodiment 2
Modification to CNT (CNTs), present inventor have studied to be modified using silane coupler
Handle and be modified processing only with acidifying, present invention protection uses silane coupler modified CNTs/CFDSF/AG-80 epoxies
The preparation method of resin composite materials；
A kind of preparation method for preparing silane coupler modified CNTs/CFDSF/AG-80 epoxy resin composite materials, mainly
Comprise the following steps：
1. pair CNT (CNTs) is modified processing using silane coupler
1.1) processing is modified using silane coupler to CNT (CNTs), acidification is carried out to it first：
CNTs is acidified using the mixed acid solution of concentrated nitric acid and the concentrated sulfuric acid, 3.5g CNTs are placed in 375ml dense nitre
In the mixed acid solution of acid and the concentrated sulfuric acid, wherein the volume ratio of concentrated nitric acid and the concentrated sulfuric acid is 3:1, room temperature is ultrasonically treated after 3.5h mixed
Close addition distilled water in solution to be diluted, filtered with filter membrane, appropriate distilled water diluting is continuously added after filtering, stood, take
Layer clear liquid is outwelled, and is filtered, and is repeated operation above for several times, until supernatant liquor pH value is 7 or so, membrane filtration is gone out into CNTs, put
1h is ground after putting oven drying, the CNT O-CNTs being acidified；
1.2) silane coupler modified CNTs preparation
The sufficient O-CNTs of the grinding obtained in 1g steps 1.1) is weighed, it is 3wt%'s to add 500ml mass fractions
KH550 and 0.2g dicyclohexylcarbodiimide (DCC), being ultrasonically treated 3h makes it well mixed, and stirring 5h makes it fully react,
The appropriate washes of absolute alcohol of obtained mixed solution will be reacted, to remove unreacted KH550 and DCC, filtering, drying,
1h is ground, so as to obtain silane coupler modified CNT Si-CNTs；
2. a pair carbon fiber double-layer partition fabric (CFDSF) is handled；
The characteristics of Woven Distance Fabric maximum is that a determining deviation can be formed between two parallel flat fabrics, the present invention
Using woven double-layer partition fabric, connected between fabric upper layer 1 and cutting optimal 2 as shown in Figure 1 by binder yarn 3, by modification
CNTs/AG-80 epoxy-resin systems solution pours the composite for being cured to and the present invention being obtained in the space fabric；In the present invention
In due to using the specification of mould 1 as 14cm × 14.5cm, it requires specification that all CFDSF fabrics cut for 14cm ×
14.5cm；
The carbon fiber double-layer partition fabric weaved, cut in advance is subjected to surface clean and surface modification treatment, that is, existed
At room temperature, the carbon fiber double-layer partition fabric cut is placed in ultrasonic cleaning solution after carrying out immersion 1.5h and washs 40min,
Wherein ultrasonic cleaning solution is that 10wt% ethanol solutions and 20wt% acetone solns press volume 1:1 mixed liquor, Ran Houqu
Go out and dried under the conditions of 105 DEG C, a certain amount of matter containing absolute ethyl alcohol for being dissolved in water is coated on double-layer partition fabric after drying
The Silane coupling agent KH550 solution that percentage is 2wt% is measured, places 30h at room temperature, so that ethanol volatilization is complete, is sealed up for safekeeping stand-by；
3. CFDSF is poured preparation modified CNTs/AG-80 epoxy-resin systems solution and heat cure
By AG-80 epoxy resin, hexahydrophthalic anhydride curing agent, 2,4,6- bis aminomethyl phenol accelerator, third
Ketone and absolute ethyl alcohol diluent, it is respectively placed in 42 DEG C of baking oven and preheats 1.5 hours, weigh 1.5g and account for epoxy resin 2.5wt%
And the sufficiently modified carbon nano-tube after the step 1.2) processing is ground, place it in proper amount of acetone solution at ultrasonic wave
After managing 1h, poured into by proportioning in epoxy resin, after 40 DEG C are stirred 5h, be ultrasonically treated after 2.5h and vacuumize 2.5h at 85 DEG C, connect
And pour into the curing agent, accelerator, diluent successively, the AG-80 epoxy resin, curing agent, the ratio of diluent are
45wt%：40wt%:15wt%, the volume ratio of absolute ethyl alcohol and acetone is 1 in the diluent:1, then mixed solution is existed
45 DEG C are sufficiently stirred 1h, and 70 DEG C vacuumize 1h, obtain being modified CNTs/AG-80 epoxy-resin systems solution；Then put in a mold
The carbon fiber double-layer partition fabric after step 2 processing is put, appropriate methyl-silicone oil is coated, pours above-mentioned modified CNTs/AG-80
Whole mould is vacuumized into 1.5h after epoxy-resin systems solution, stands 42h, it is then compound according to pure CNTs/CFDSF/AG-80
80 DEG C/0.5h → 110 DEG C of curing process/0.5h → 120 DEG C/4h → 150 DEG C of material/4h carries out heat cure, is obtained through cooling
Silane coupler modified CNTs/CFDSF/AG-80 epoxy resin composite materials.
Embodiment 3
Modification to CNT (CNTs), present inventor have studied to be modified using silane coupler
Handle and be modified processing only with acidifying, present invention protection uses silane coupler modified CNTs/CFDSF/AG-80 epoxies
The preparation method of resin composite materials；
A kind of preparation method for preparing silane coupler modified CNTs/CFDSF/AG-80 epoxy resin composite materials, mainly
Comprise the following steps：
1. pair CNT (CNTs) is modified processing using silane coupler
1.1) processing is modified using silane coupler to CNT (CNTs), acidification is carried out to it first：
CNTs is acidified using the mixed acid solution of concentrated nitric acid and the concentrated sulfuric acid, 5g CNTs are placed in 500ml concentrated nitric acid
In the mixed acid solution of the concentrated sulfuric acid, wherein the volume ratio of concentrated nitric acid and the concentrated sulfuric acid is 4:It is molten in mixing after 1, room temperature supersound process 4h
Distilled water is added in liquid to be diluted, and is filtered with filter membrane, appropriate distilled water diluting is continuously added after filtering, stood, take upper strata clear
Liquid is outwelled, and is filtered, and repeats operation above for several times, until supernatant liquor pH value is 7 or so, membrane filtration is gone out into CNTs, places baking
Case grinds 1h after drying, the CNT O-CNTs being acidified；
1.2) silane coupler modified CNTs preparation
The sufficient O-CNTs of the grinding obtained in 2g steps 1.1) is weighed, it is 4wt%'s to add 750ml mass fractions
KH550 and 0.25g dicyclohexylcarbodiimide (DCC), being ultrasonically treated 2.5h makes it well mixed, and stirring 6h makes it fully anti-
Should, the appropriate washes of absolute alcohol of obtained mixed solution will be reacted, to remove unreacted KH550 and DCC, filtering, is done
It is dry, 1h is ground, so as to obtain silane coupler modified CNT Si-CNTs；
2. a pair carbon fiber double-layer partition fabric (CFDSF) is handled；
The characteristics of Woven Distance Fabric maximum is that a determining deviation can be formed between two parallel flat fabrics, the present invention
Using woven double-layer partition fabric, connected between fabric upper layer 1 and cutting optimal 2 as shown in Figure 1 by binder yarn 3, by modification
CNTs/AG-80 epoxy-resin systems solution pours the composite for being cured to and the present invention being obtained in the space fabric；In the present invention
In due to using the specification of mould 1 as 14cm × 14.5cm, it requires specification that all CFDSF fabrics cut for 14cm ×
14.5cm；
The carbon fiber double-layer partition fabric weaved, cut in advance is subjected to surface clean and surface modification treatment, that is, existed
At room temperature, the carbon fiber double-layer partition fabric cut is placed in ultrasonic cleaning solution after carrying out immersion 1.5h and washs 40min,
Wherein ultrasonic cleaning solution is that 10wt% ethanol solutions and 20wt% acetone solns press volume 1:1 mixed liquor, Ran Houqu
Go out and dried under the conditions of 105 DEG C, a certain amount of matter containing absolute ethyl alcohol for being dissolved in water is coated on double-layer partition fabric after drying
The Silane coupling agent KH550 solution that percentage is 2wt% is measured, places 30h at room temperature, so that ethanol volatilization is complete, is sealed up for safekeeping stand-by；
3. CFDSF is poured preparation modified CNTs/AG-80 epoxy-resin systems solution and heat cure
By AG-80 epoxy resin, hexahydrophthalic anhydride curing agent, 2,4,6- bis aminomethyl phenol accelerator, third
Ketone and absolute ethyl alcohol diluent, it is respectively placed in 45 DEG C of baking oven and preheats 2 hours, weigh 2.7g and account for epoxy resin 4.5wt% simultaneously
The modified carbon nano-tube sufficiently after the step 1.2) processing is ground, places it in ultrasonication in proper amount of acetone solution
After 1h, poured into by proportioning in epoxy resin, after 45 DEG C are stirred 4h, be ultrasonically treated after 3h and vacuumize 3h at 90 DEG C, then successively
The curing agent, accelerator, diluent are poured into, the AG-80 epoxy resin, curing agent, the ratio of diluent are 50wt%：
45wt%:5wt%, the volume ratio of absolute ethyl alcohol and acetone is 1 in the diluent:1.5, then mixed solution is filled at 50 DEG C
Divide stirring 1h, 75 DEG C vacuumize 1h, obtain being modified CNTs/AG-80 epoxy-resin systems solution；Described in then placing in a mold
Carbon fiber double-layer partition fabric after step 2 processing, coats appropriate methyl-silicone oil, pours above-mentioned modified CNTs/AG-80 asphalt mixtures modified by epoxy resin
Whole mould is vacuumized into 2h after resin system solution, stands 48h, then consolidating according to pure CNTs/CFDSF/AG-80 composites
80 DEG C/0.5h → 110 DEG C of chemical industry skill/0.5h → 120 DEG C/4h → 150 DEG C/4h carries out heat cure, is obtained through cooling silane coupled
Agent is modified CNTs/CFDSF/AG-80 epoxy resin composite materials.
Carbon fiber double-layer partition fabric in above example 1-3 employed in step 2 is that upper and lower surface layer is plain weave group
Woven fabric, twill, satin weave or other fabric groups can also be used certainly for the fabric tissue of the carbon fiber double-layer partition fabric
Knit the two-layer fabric of structure.
The silane coupler modified CNTs/CFDSF/AG-80 epoxy resin composite materials heating power prepared below to the present invention
Learn performance and electric conductivity carries out testing research.
1. the research of silane coupler modified CNTs/CFDSF/AG-80 composite impacts section
If Fig. 2 a, 2b are that Si-CNTs/CFDSF/AG-80 composite impacts are broken when Si-CNTs contents are 2.5% respectively
The scanning electron microscope (SEM) photograph in face dimple area and impact fracture surface river area；It can be seen that Si-CNTs/CFDSF/AG-80 systems from Fig. 2 a
Dimple area in flap it is concavo-convex, unit area dimple number is more.It can be seen that the system composite section from Fig. 2 b
River pattern it is finer and closely woven, and major diameter is bigger, it can be seen that can be with the white extract of Anticrack, these all illustrate
Toughening effects of the Si-CNTs to composite system.
2. silane coupler modified CNTs/CFDSF/AG-80 is modified the dynamic force of CNTs/CFDSF/AG-80 composites
Learn performance study
Dynamic mechanical analysis is a kind of means of testing for testing high molecular polymer mechanical performance.Pass through dynamic mechanical analysis
The dynamic storage modulus E ' and loss modulus E " of composite can be drawn.E ' and E " can be used for characterizing respectively the rigidity of material with
And the viscosity component of material, the loss modulus of material are typically represented with tan δ, as E " and E ' ratio.
If Fig. 3 a, 3b are the storage modulus E ' and loss modulus of Si-CNTs/CFDSF/AG-80 composite systems respectively
E " dynamic analysis figure.It can be seen that with the gradual increase of temperature, the energy storage mould of Si-CNTs/CFDSF/AG-80 systems
Amount E ' can be gradually decreased, and in room temperature to reduce between 100 DEG C and unobvious, and its loss modulus E " can fall after rising.Work as Si-
The storage modulus E ' of Si-CNTs/CFDSF/AG-80 systems is smaller when CNTs content is 4.5%, illustrates that its rigidity is small, simultaneously
Its loss modulus E " is larger, illustrates that its toughness is preferable；And its loss modulus E " is maximum when Si-CNTs content is 2.5%, say
The toughness of the bright system is preferable, and this illustrates that silane coupler modified CNTs has certain toughening effect to epoxy resin.
3. the thermodynamics test analysis of silane coupler modified CNTs/CFDSF/AG-80 composites
During the thermal property of composite refers mainly to use, respective response is made to environment temperature, so as to show
Different thermal properties, be one of important performance of composite, by analyze the initial and maximum heat decomposition temperature of system from
And obtain the stability of composite thermal property.As shown in Fig. 4 a, 4b, it is Si-CNTs/CFDSF/AG-80 systems respectively
Thermal weight loss TG curves and DTG curves.On the whole, with the increase of Si-CNTs contents, Si-CNTs/CFDSF/AG-80 bodies
The initial and maximum heat decomposition temperature of system has the trend gradually lifted, and overall heat-resisting effect is good.Due to inorganic matter
All more heat-resisting, so after adding Si-CNTs, its temperature capability can increase.
4. the electrical performance testing analysis of silane coupler modified CNTs/CFDSF/AG-80 composites
It is the volume electricity of silane coupler modified CNTs composites Si-CNTs/CFDSF/AG-80 systems as shown in Figure 5
Resistance rate, curve can be seen that when modified CNTs contents are continuously increased from figure, the body of the epoxy resin-matrix system full of CNTs
Product resistivity can be reduced constantly, and its specific insulation is higher when CNTs contents are also smaller, now because CNTs disperses
Comparison open, contact can not be formed between CNTs, electronics is difficult to be moved between adjacent particles, to the cooperative effect of CF conductive networks
It is weaker.With the further increase of modified CNTs contents, the resistivity-CNTs content curves of composite occur that one is dashed forward
Become, now specific insulation can decline by a relatively large margin, show that CNTs contents have reached percolation threshold.Now most CNTs
Between spacing it is sufficiently small or phase mutual contact, so as to form CNTs conductive networks, to the association of CF conductive networks
Strengthen with effect, so that the specific insulation of composite is undergone mutation.With the further increase of modified CNTs contents,
After percolation threshold, the change of the resistivity of composite all tends towards stability again, illustrates that conductive path has been formed, modified
Contacted between CNTs or electronics can move freely to form conductive network, now resistivity is difficult to vary widely.
Embodiment for technical solution of the present invention and experiment institute test result above, for those skilled in the art
These embodiments are changed, changed, replaced, integrated and work by speech without departing from the principles and spirit of the present invention
Skill parameter modification is each fallen within protection scope of the present invention.
Claims (7)
1. a kind of preparation method of silane coupler modified CNTs/CFDSF/AG-80 epoxy resin composite materials, its feature exist
In the preparation method specifically includes following steps：
(1) CNTs is acidified using the mixed acid solution of concentrated nitric acid and the concentrated sulfuric acid, 2~5g CNTs is placed in 250~500ml
Concentrated nitric acid and the concentrated sulfuric acid mixed acid solution in, wherein the volume ratio of concentrated nitric acid and the concentrated sulfuric acid be 3:1~4:1, room temperature ultrasound at
Distilled water is added in mixed solution to be diluted, filtered with filter membrane, it is dilute that appropriate distilled water is continuously added after filtering after 3~4h of reason
Release, stand, take supernatant liquor to outwell, filter, repeat operation above for several times, until supernatant liquor pH value is 7 or so, by filter membrane mistake
CNTs is filtered out, 0.5~1h, the CNT O-CNTs being acidified are ground after placing oven drying；
(2) silane coupler modified CNTs preparation, the sufficient O-CNTs of grinding that a certain amount of step (1) obtains is weighed, is added
Enter appropriate KH550 and DCC, being ultrasonically treated makes it well mixed for 2~3 hours, and 4~6h of stirring makes it fully react, and will react
The appropriate washes of absolute alcohol of the mixed solution arrived, to remove unreacted KH550 and DCC, filtering, dry, grinding 0.5~
1h, so as to obtain silane coupler modified CNT Si-CNTs；
(3) carbon fiber double-layer partition fabric (CFDSF) is handled, the carbon fiber double-layer partition that will in advance weave, cut
Fabric carries out surface clean and surface modification treatment, concrete technology are：At room temperature, the carbon fiber double-layer partition cut is knitted
Thing, which is placed in ultrasonic cleaning solution, to carry out washing 30~50min after 1~2h of immersion, then takes out and is done under the conditions of 95~110 DEG C
It is dry, coated after drying on double-layer partition fabric a certain amount of mass percent containing absolute ethyl alcohol for being dissolved in water for 1.5~
3wt% Silane coupling agent KH550 solution, 24h~36h is placed at room temperature, so that ethanol volatilization is complete, seal up for safekeeping stand-by；
(4) prepare modified CNTs/AG-80 epoxy-resin systems solution to pour CFDSF and heat cure, by AG-80 epoxies
Resin, hexahydrophthalic anhydride curing agent, 2,4,6- bis aminomethyl phenol accelerator, acetone and absolute ethyl alcohol diluent,
It is respectively placed in 38~45 DEG C of baking oven and preheats 1~2 hour, weighs 0.3~2.7g and account for 0.5~4.5wt% of epoxy resin and grind
The modified carbon nano-tube Si-CNTs sufficiently after the step (2) processing is ground, places it in ultrasonic wave in proper amount of acetone solution
After handling 0.5~1h, pour into epoxy resin by proportioning, after 35~45 DEG C are stirred 4~6h, be ultrasonically treated after 2~3h 80
~90 DEG C vacuumize 2~3h, after then pouring into the curing agent, accelerator, diluent successively, by mixed solution at 40~50 DEG C
0.5~1h is sufficiently stirred, 65~75 DEG C vacuumize 0.5~1h, obtain being modified CNTs/AG-80 epoxy-resin systems solution；Then
The carbon fiber double-layer partition fabric after the step (3) processing is placed in a mold, is coated appropriate methyl-silicone oil, is poured above-mentioned change
Property CNTs/AG-80 epoxy-resin systems solution after whole mould vacuumized into 1~2h, 36~48h is stood, then in a constant temperature
Heat cure is carried out under degree time conditions, silane coupler modified CNTs/CFDSF/AG-80 epoxy resin composite wood is obtained through cooling
Material.
2. the preparation of silane coupler modified CNTs/CFDSF/AG-80 epoxy resin composite materials according to claim 1
Method, it is characterised in that the sufficient O-CNTs of grinding that 1~3g obtains through the step (1) is weighed in the step (2), is added
Enter KH550 and 0.2~0.3g that appropriate 500~1000ml mass fractions are 3wt%~5wt% DCC, it is small to be ultrasonically treated 2~3
When make it well mixed, 4~6h of stirring makes it fully react.
3. the preparation of silane coupler modified CNTs/CFDSF/AG-80 epoxy resin composite materials according to claim 1
Method, it is characterised in that ultrasonic cleaning solution described in the step (3) be 10~30wt% ethanol solutions and 20~
40wt% acetone solns press volume 1:1~1:1.5 mixed liquor.
4. the silane coupler modified CNTs/CFDSF/AG-80 epoxy resin composite wood according to claim any one of 1-3
The preparation method of material, it is characterised in that in the step (4), the AG-80 epoxy resin, curing agent, the ratio of diluent are
45~50wt%：40~45wt%:5~15wt%, the volume ratio of absolute ethyl alcohol and acetone is 1 in the diluent:1~1:
1.5。
5. according to any one of the claim 1-3 silane coupler modified CNTs/CFDSF/AG-80 epoxy resin composite materials
Preparation method, it is characterised in that the heat cure in the step (4) is according to pure CNTs/CFDSF/AG-80 composites
80 DEG C/0.5h → 110 DEG C of curing process/0.5h → 120 DEG C/4h → 150 DEG C/4h carries out heat cure.
6. the silane coupler modified CNTs/CFDSF/AG-80 epoxy resin composite wood according to claim any one of 1-3
The preparation method of material, it is characterised in that be that the carbon fiber double-layer partition fabric is that upper and lower surface layer is flat in the step (3)
Line tissue fabric.
7. the silane coupler modified CNTs/CFDSF/AG-80 epoxy resin composite wood according to claim any one of 1-3
The preparation method of material, it is characterised in that the modified carbon nano-tube in the step (4) account for epoxy resin 2.5~
4.5wt%.
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| CN113831598A (en) * | 2021-10-29 | 2021-12-24 | 江苏芬茂新材料科技有限公司 | Modified carbon nanotube and application thereof in special plastic for automobile fuel tank |
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