CN107987482A - Solvent-free graphene/carbon nano-tube/ferroso-ferric oxide three-dimensional composite Nano fluid epoxy resin and preparation method - Google Patents
Solvent-free graphene/carbon nano-tube/ferroso-ferric oxide three-dimensional composite Nano fluid epoxy resin and preparation method Download PDFInfo
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Abstract
The present invention relates to a kind of solvent-free graphene/carbon nano-tube/Fe3O4Three-dimensional composite Nano fluid orients reinforced epoxy composite material, makes graphene oxide and acidifying carbon nanotubes compound by π pi bonds first, then prepares Fe by coprecipitation3O4, graphene oxide and acidifying carbon nano tube surface are grafted on, obtains having magnetic graphene/carbon nano-tube/Fe3O4Three-dimensional composite nanoparticle.With graphene/carbon nano-tube/Fe3O4Three-dimensional composite nanoparticle is core, by covalent bond grafted silane coupling agent and polyethers amine oligomer double-decker, makes it that liquid condition closely be presented under room temperature, is added in epoxy resin solidifying system and cures, and obtains orientation reinforced epoxy composite material.Preparation method of the present invention is simple, easy so that graphene and the carbon nanotubes being attached on graphene can realize and align that the mechanical property and thermal property to epoxy resin have certain lifting in the epoxy.
Description
Technical field
The present invention relates to a kind of solvent-free graphene/carbon nano-tube/Fe3O4Three-dimensional composite Nano fluid orients reinforced epoxy
Resin composite materials, can effectively improve the mechanics and thermal property of resin matrix, can be applied to the performance of polymer matrix composites
It is modified.
Background technology
Graphene can be used as Nano filling reinforced resin material with carbon nanotubes, both are compound can to combine sheet graphene
With the modified effect of wire carbon nanotubes, if it is possible to align, it is more effective for the modified effect of polymer.But will
Orient both, it is necessary under certain field action.Carbon nanotubes and graphene all have certain electric conductivity, can apply electricity
, align it, but due to needing to heat during resin solidification, apply electric field under the environment of heat, ratio is operated in technique
It is more complicated.It is simpler in technique, feasible if oriented under magnetic field.By Fe3O4It is deposited on graphene oxide/carbon nanotubes
On, make nano-particle that there is magnetism, the fast and effectively response characteristic under magnetic field condition can be by graphene oxide/carbon nanometer
Pipe aligns in resin matrix.But in common method of modifying, the nano-particle such as carbon nanotubes and graphene is in solid
State, is difficult to realize single dispersing in resin material, have impact on and aligns effect in magnetic field.
The content of the invention
Technical problems to be solved
In order to avoid the shortcomings of the prior art, the present invention proposes a kind of solvent-free graphene/carbon nano-tube/Fe3O4Three
Tie up composite Nano fluid orientation reinforced epoxy composite material.It has developed to improve dispersiveness and interface performance, the present invention
One kind Fe containing nanoscale3O4, carbon nanotubes, the three-dimensional composite nanoparticle of graphene film Rotating fields, mass percentage is more than
The solvent-free nanometer fluid of 6wt%, and it is added into mass fraction under 0.5~1T weak magnetic field actions in epoxy systems
The three-dimensional compound solvent-free nanometer fluid of 0.5-2wt%, can realize three-dimensional composite nanoparticle orientation row in the epoxy
Row, mechanical property and thermal property to the epoxide resin material after curing have certain lifting.
Technical solution
A kind of solvent-free graphene/carbon nano-tube/Fe3O4Three-dimensional composite Nano fluid orients reinforced epoxy composite wood
Material, it is characterised in that component is:25~35 mass parts amine curing agents and matter are added in the liquid-state epoxy resin that quality is 100 parts
Measure solvent-free graphene/carbon nano-tube/Fe that part is 0.1~33O4Three-dimensional composite Nano fluid;The solvent-free graphene/carbon
Nanotube/Fe3O4Three-dimensional composite Nano fluid is by graphene/carbon nano-tube/Fe3O4As core, coronal layer silane coupling agent and neck
Shape strata ether amines M2070 is formed as shell;The graphene uses graphene oxide;The carbon nanotubes is using acidifying carbon nanometer
Pipe;The graphene oxide:It is acidified carbon nanotubes:Fe3O4The mass ratio of three-dimensional composite nanoparticle is 1~2:1~3:1~4;
The coronal layer silane coupling agent: the mass ratio of neck-shaped strata ether amines M2070 is 6.84: 60;The graphene/carbon nano-tube/
Fe3O4Mass ratio with shell is 6~20:94~80.
The liquid-state epoxy resin is less than 50-55 DEG C of epoxy resin for softening point.
The curing agent is room temperature amine curing agent.
The Fe3O4Nano-particle average diameter 8nm.
One kind prepares the solvent-free graphene/carbon nano-tube/Fe3O4Three-dimensional composite Nano fluid orients reinforced epoxy tree
The method of resin composite material, it is characterised in that step is as follows:
Step 1, graphene/carbon nano-tube/Fe3O4The preparation of compound:
Graphene oxide, acidifying carbon nanotubes are prepared using He Mosi methods, oxygen is formed by the method that ultrasound is mixed
Graphite alkene/carbon nanotubes composite nanoparticle;
Using coprecipitation in graphene oxide/carbon nanotubes composite nanoparticle deposition Fe3O4, using centrifuge and
Magnetic field is separated off not depositing Fe3O4Nano-particle, formed graphene/carbon nano-tube/Fe3O4Three-dimensional composite nanoparticle;
Step 2, solvent-free graphene/carbon nano-tube/Fe3O4Three-dimensional composite Nano fluid:Pass through epoxy in silane coupling agent
Base reacts to form neck-shaped layer and coronal layer with polyetheramine Amino End Group, then is connect by the hydrolysis of silane coupling agent other end silica methyl
Branch forms solvent-free graphene/carbon nano-tube/Fe in nanoparticle surface3O4Three-dimensional composite Nano fluid;
Step 3, solvent-free graphene/carbon nano-tube/Fe3O4The epoxy resin of three-dimensional composite Nano fluid orientation enhancing is received
Nano composite material:By solvent-free graphene/carbon nano-tube/Fe3O4Three-dimensional composite Nano fluid proportionally adds Breakup of Liquid Ring oxygen tree
In fat, curing agent is added, completes to cure under 0.5~1T magnetic field conditions, obtains solvent-free graphene/carbon nano-tube/Fe3O4
The epoxy resin nano composites of three-dimensional composite Nano fluid orientation enhancing.
The step 1 graphene/carbon nano-tube/Fe3O4The preparation of three-dimensional composite nanoparticle is:It is 1 by mass ratio:1
Acidifying carbon nanotubes and graphene oxide are dissolved in the methanol that mass ratio is 200, and room temperature is stirred by ultrasonic to obtain black suspension;Will
Concentration is 0.224g/mL ferric chloride hexahydrates FeCl3·6H2O is dissolved in deionized water, adds in above-mentioned black suspension, room temperature
It is 0.165g/mL frerrous chloride tetrahydrates FeCl that concentration is added after ultrasonic agitation2·4H2O aqueous solution 20mL, room temperature ultrasound
The ammonium hydroxide that mass ratio is 60 is added after stirring, room temperature is stirred by ultrasonic to obtain black suspension;By above-mentioned suspension after the completion of reaction
Centrifugation, takes lower sediment, is cleaned repeatedly with deionized water and be precipitated to neutrality, obtain graphene/carbon nano-tube/Fe3O4It is three-dimensional compound
Nano-particle.
Solvent-free graphene/carbon nano-tube/the Fe of step 23O4The preparation of three-dimensional composite Nano fluid is:Contained with end
For the silane coupling agent KH560 of epoxy group as neck-shaped layer, coronal layer is adopted as the oligomer polyetheramine M2070 with Amino End Group,
Both mass ratioes are 6.84:60, be dissolved in 600mL methanol, magnetic agitation, stir under the conditions of 45-60 DEG C 12-18 it is small when,
The upper Amino End Groups of M2070 form covalent bond with epoxy group on KH560, add graphene/carbon nano-tube/Fe3O4Three-dimensional composite Nano
Particle, after the completion of stirring reaction, unreacted graphene/carbon nano-tube/Fe is removed with supercentrifuge3O4Three-dimensional composite Nano
Particle, takes supernatant liquid dialysis drying to obtain black non transparent liquid, is solvent-free graphene/carbon nano-tube/Fe3O4It is three-dimensional
Composite Nano fluid.
Solvent-free graphene/carbon nano-tube/Fe of the step 33O4The asphalt mixtures modified by epoxy resin of three-dimensional composite Nano fluid orientation enhancing
The preparation of resin nano composite material:Using epoxy resin as matrix, the amine of ambient temperature curable is as curing agent, in 100 parts of rings
25~35 parts of amine curing agents and 0.1~3 part of solvent-free graphene/carbon nano-tube/Fe are added in oxygen tree fat3O4It is three-dimensional compound
Nano-fluid, ultrasound 0.3-0.5h, is placed in vacuum drying chamber and vacuumizes after stirring evenly, and is poured into after exclusion bubble ready
In mould, 0.5-1T magnetic fields are inserted in mould both sides, after curing 24-30h at 70~80 DEG C, obtain solvent-free graphene/carbon
Nanotube/Fe3O4The epoxy resin nano composites of three-dimensional composite Nano fluid orientation enhancing.
Beneficial effect
A kind of solvent-free graphene/carbon nano-tube/Fe proposed by the present invention3O4Three-dimensional composite Nano fluid orientation enhancing ring
Epoxy resin composite material, using graphene oxide and acidifying carbon nanotubes, makes graphene oxide lead to acidifying carbon nanotubes first
It is compound to cross pi-pi bond, Fe is then prepared by coprecipitation3O4, graphene oxide and acidifying carbon nano tube surface are grafted on,
Obtain having magnetic graphene/carbon nano-tube/Fe3O4Three-dimensional composite nanoparticle.With graphene/carbon nano-tube/Fe3O4Three
Dimension composite nanoparticle is core, passes through covalent bond grafted silane coupling agent and the double-deck knot of polyetheramine (KH560-M2070) oligomer
Structure, makes it that liquid condition closely be presented under room temperature, is added in epoxy resin solidifying system, in 0.5~1T magnetic field conditions
Lower curing, obtains orientation reinforced epoxy composite material, and three-dimensional composite nanoparticle can realize single point in the epoxy
Dissipate and multidimensional aligns.Graphene/carbon nano-tube/Fe of the present invention3O4Three-dimensional composite nanoparticle orients reinforced epoxy
Composite material and preparation method thereof is simple, easy, since three-dimensional composite nanoparticle is in a liquid state below 35 DEG C, single dispersing, and have
It is magnetic so that graphene and the carbon nanotubes being attached on graphene can in the epoxy be realized and aligned, to epoxy
The mechanical property and thermal property of resin have certain lifting.
The present invention is by graphene/carbon nano-tube/Fe3O4Composite surface is grafted long-chain organic matter, prepares in nearly room
There is solvent-free graphene/carbon nano-tube/Fe of fluid characteristics under temperature, condition of no solvent3O4Three-dimensional composite Nano fluid, this
Method of modifying can improve dispersiveness of the nano-particle in resin matrix, solve the agglomeration traits of nano-particle, improve nanometer
The compatible problem of particle and resin matrix, at the same have magnetic solvent-free three-dimensional composite Nano fluid can be real under magnetic field
Now align, obtain the polymer matrix composites of the three-dimensional composite nanoparticle enhancing of orientable arrangement, give full play to three-dimensional
The performance of composite nanoparticle is notable to the modified effect of polymer.
The present invention compared with prior art the advantages of be:
Obtained solvent-free nanometer fluid has the modified effect of solid nano filler and the mobility of liquid concurrently and disperses
Property, the nano-particle in obtained nanoreinforcement material is realized single dispersing and can be aligned under magnetic fields so that increases
Strong epoxy resin composite material has more preferable mechanical property and heat conductivility.
Brief description of the drawings
Fig. 1:Flow chart of the present invention
Embodiment
In conjunction with embodiment, attached drawing, the invention will be further described:
The present invention technological thought be:
Received in solvent-free three-dimensional composite Nano fluid in the present invention containing graphene/carbon of the mass fraction more than 6-20%
Mitron/Fe3O4Composite nanoparticle, mass fraction form for 80~94% oligomer, and oligomer grafts on graphite by covalent bond
Alkene/carbon nanotubes/Fe3O4Nanoparticle surface, oligomer are made of silane coupling agent and polyetheramine M2070, are referred to as neck-shaped
Layer and coronal layer.
Graphene oxide, acidifying carbon nanotubes used in the present invention are prepared using He Mosi methods.
The Fe that the present invention is deposited3O4Nano-particle is prepared using coprecipitation, average diameter 8nm.
Silane coupling agent used in the present invention is silane coupling agent KH560 of the end containing epoxy group, as neck-shaped layer.
Oligomer used in the present invention is the oligomer polyetheramine M2070 with Amino End Group, as coronal layer.
Epoxy resin used in the present invention is liquid epoxy resin.
Curing agent used in the present invention is amine, acid anhydride type curing agent.
A kind of solvent-free graphene/carbon nano-tube/Fe of the present invention3O4Three-dimensional composite Nano fluid orients reinforced epoxy tree
The preparation method of resin composite material, carries out in the steps below.
The present invention prepares graphene oxide, acidifying carbon nanotubes, the method by the way that ultrasound is mixed using He Mosi methods
Graphene oxide/carbon nanotubes composite nanoparticle is formed, using coprecipitation in graphene oxide/carbon nanotubes composite Nano
Particle deposition Fe3O4, it is separated off not depositing Fe with magnetic field using centrifuging3O4Nano-particle, formed graphene/carbon receive
Mitron/Fe3O4Three-dimensional composite nanoparticle.React to form neck-shaped layer by silane coupling agent epoxy group and polyetheramine Amino End Group
With coronal layer, then nanoparticle surface is grafted on by the hydrolysis of silane coupling agent other end silica methyl, forms solvent-free stone
Black alkene/carbon nanotubes/Fe3O4Three-dimensional composite Nano fluid.Solvent-free three-dimensional composite Nano fluid is added into liquid according to different proportion
In body epoxy resin, curing agent is proportionally added, completes to cure under 0.5~1T magnetic field conditions.
The preparation method of the present invention is shown in attached drawing (by taking polyethers amine hardener D230 as an example)
Embodiment 1:
Graphene/carbon nano-tube/Fe3O4The preparation of compound:0.5g is acidified carbon nanotubes and 0.5g graphene oxides are molten
In 50mL methanol, room temperature ultrasonic agitation 1h, obtains black suspension.By 4.48g ferric chloride hexahydrates (FeCl3·6H2O)
A certain amount of deionized water is dissolved in, is added in above-mentioned black suspension, room temperature ultrasonic agitation 0.5h, then by 1.65g frerrous chlorides four
Hydrate (FeCl2·4H2O a certain amount of deionized water) is dissolved in, is added in reaction solution, room temperature ultrasonic agitation 0.2h, adds afterwards
30g ammonium hydroxide, room temperature ultrasonic agitation 1h, obtains black suspension.Above-mentioned suspension is centrifuged after the completion of reaction, takes lower sediment,
Cleaned repeatedly with deionized water and be precipitated to neutrality, obtain graphene/carbon nano-tube/Fe3O4Compound.
Selecting silane coupling agent KH560 of the end containing epoxy group, coronal layer is adopted as with Amino End Group as neck-shaped layer
Oligomer polyetheramine M2070, adds 3.42g KH560 and 30g M2070, magnetic agitation, under the conditions of 45 DEG C in 300mL methanol
Stir 12 it is small when, the upper epoxy group formation covalent bond of the upper Amino End Groups of M2070 and KH560, adds above-mentioned preparation in above-mentioned solution
Graphene/carbon nano-tube/Fe3O4Compound, continue stirring 6 it is small when, remove unreacted stone with supercentrifuge after the completion of reaction
Black alkene/carbon nanotubes/Fe3O4Compound, takes supernatant liquid dialysis drying to obtain black non transparent liquid, is that graphene/carbon is received
Mitron/Fe3O4Solvent-free nanometer fluid.
Selecting E51 epoxy resin, for polyetheramine D230 as curing agent, curing accelerator is three-(dimethylamino as matrix
Methyl) phenol DMP-30.18g D230 and 1.2g DMP-30 and 0.8g graphene/carbon nanometers are added in 60g E51 resins
Pipe/Fe3O4Solvent-free nanometer fluid, ultrasound 0.5h after stirring evenly, is placed in vacuum drying chamber after vacuumizing 0.5h exclusion bubbles
Pour into ready mould, 0.6T magnetic fields are inserted in mould both sides, graphene/carbon nanometer is obtained after curing 24h at 70 DEG C
Pipe/Fe3O4The epoxy resin nano composites of solvent-free nanometer fluid orientation enhancing.
Embodiment 2:
Graphene/carbon nano-tube/Fe3O4The preparation of compound:0.5g is acidified carbon nanotubes and 0.5g graphene oxides are molten
In 50mL methanol, room temperature ultrasonic agitation 1h, obtains black suspension.By 2.24g ferric chloride hexahydrates (FeCl3·6H2O)
A certain amount of deionized water is dissolved in, is added in above-mentioned black suspension, room temperature ultrasonic agitation 0.5h, then by 0.83g frerrous chlorides four
Hydrate (FeCl2·4H2O a certain amount of deionized water) is dissolved in, is added in reaction solution, room temperature ultrasonic agitation 0.2h, adds afterwards
15g ammonium hydroxide, room temperature ultrasonic agitation 1h, obtains black suspension.Above-mentioned suspension is centrifuged after the completion of reaction, takes lower sediment,
Cleaned repeatedly with deionized water and be precipitated to neutrality, obtain graphene/carbon nano-tube/Fe3O4Compound.
Selecting silane coupling agent KH560 of the end containing epoxy group, coronal layer is adopted as with Amino End Group as neck-shaped layer
Oligomer polyetheramine M2070, adds 2.28g KH560 and 20g M2070, magnetic agitation, under the conditions of 45 DEG C in 300mL methanol
Stir 12 it is small when, the upper epoxy group formation covalent bond of the upper Amino End Groups of M2070 and KH560, adds above-mentioned preparation in above-mentioned solution
Graphene/carbon nano-tube/Fe3O4Compound, continue stirring 6 it is small when, remove unreacted stone with supercentrifuge after the completion of reaction
Black alkene/carbon nanotubes/Fe3O4Compound, takes supernatant liquid dialysis drying to obtain black non transparent liquid, is that graphene/carbon is received
Mitron/Fe3O4Solvent-free nanometer fluid.
Selecting epoxy resin E51, acid anhydride type curing agent methyl tetrahydro phthalic anhydride is as curing agent, curing accelerator as matrix
For three-(dimethylamino methyl) phenol DMP-30.48g methyl tetrahydro phthalic anhydrides and 0.6g DMP-30 are added in 60g E51 resins
And 1.1g graphene/carbon nano-tubes/Fe3O4Solvent-free nanometer fluid, ultrasound 0.5h, is placed on vacuum drying chamber after stirring evenly
Inside vacuumize 0.5h exclude bubble after pour into ready mould, insert 0.6T magnetic fields in mould both sides, 90 DEG C, 100 DEG C,
Graphene/carbon nano-tube/Fe is obtained after curing 1.5h, 0.5h, 0.5h, 0.5h, 1.5h at 110 DEG C, 120 DEG C, 140 DEG C respectively3O4
Solvent-free nanometer fluid orients reinforced epoxy based nano composite material.
All just the same before above-mentioned two example, only neck-shaped layer and coronal layer is different.
Claims (8)
- A kind of 1. solvent-free graphene/carbon nano-tube/Fe3O4Three-dimensional composite Nano fluid orients reinforced epoxy composite material, It is characterized in that component is:25~35 mass parts amine curing agents and quality are added in the liquid-state epoxy resin that quality is 100 parts Part is 0.1~3 solvent-free graphene/carbon nano-tube/Fe3O4Three-dimensional composite Nano fluid;The solvent-free graphene/carbon is received Mitron/Fe3O4Three-dimensional composite Nano fluid is by graphene/carbon nano-tube/Fe3O4As core, coronal layer silane coupling agent and neck-shaped Strata ether amines M2070 is formed as shell;The graphene uses graphene oxide;The carbon nanotubes is using acidifying carbon nanometer Pipe;The graphene oxide:It is acidified carbon nanotubes:Fe3O4The mass ratio of three-dimensional composite nanoparticle is 1~2:1~3:1~4; The coronal layer silane coupling agent: the mass ratio of neck-shaped strata ether amines M2070 is 6.84: 60;The graphene/carbon nano-tube/ Fe3O4Mass ratio with shell is 6~20:94~80.
- 2. solvent-free graphene/carbon nano-tube/Fe according to claim 13O4Three-dimensional composite Nano fluid orientation enhancing ring Epoxy resin composite material, it is characterised in that:The liquid-state epoxy resin is less than 50-55 DEG C of epoxy resin for softening point.
- 3. solvent-free graphene/carbon nano-tube/Fe according to claim 13O4Three-dimensional composite Nano fluid orientation enhancing ring Epoxy resin composite material, it is characterised in that:The curing agent is room temperature amine curing agent.
- 4. solvent-free graphene/carbon nano-tube/Fe according to claim 13O4Three-dimensional composite Nano fluid orientation enhancing ring Epoxy resin composite material, it is characterised in that:The Fe3O4Nano-particle average diameter 8nm.
- 5. one kind prepares the solvent-free graphene/carbon nano-tube/Fe of any one described in Claims 1 to 43O4Three-dimensional composite Nano stream The method that body orients reinforced epoxy composite material, it is characterised in that step is as follows:Step 1, graphene/carbon nano-tube/Fe3O4The preparation of compound:Graphene oxide, acidifying carbon nanotubes are prepared using He Mosi methods, the method by the way that ultrasound is mixed forms oxidation stone Black alkene/carbon nanotubes composite nanoparticle;Using coprecipitation in graphene oxide/carbon nanotubes composite nanoparticle deposition Fe3O4, utilize centrifugation and magnetic field It is separated off not depositing Fe3O4Nano-particle, formed graphene/carbon nano-tube/Fe3O4Three-dimensional composite nanoparticle;Step 2, solvent-free graphene/carbon nano-tube/Fe3O4Three-dimensional composite Nano fluid:By silane coupling agent epoxy group with Polyetheramine Amino End Group reacts to form neck-shaped layer and coronal layer, then is grafted on by the hydrolysis of silane coupling agent other end silica methyl Nanoparticle surface, forms solvent-free graphene/carbon nano-tube/Fe3O4Three-dimensional composite Nano fluid;Step 3, solvent-free graphene/carbon nano-tube/Fe3O4The epoxide resin nano of three-dimensional composite Nano fluid orientation enhancing is answered Condensation material:By solvent-free graphene/carbon nano-tube/Fe3O4Three-dimensional composite Nano fluid proportionally adds liquid epoxies In, curing agent is added, completes to cure under 0.5~1T magnetic field conditions, obtains solvent-free graphene/carbon nano-tube/Fe3O4Three Tie up the epoxy resin nano composites of composite Nano fluid orientation enhancing.
- 6. according to the method described in claim 5, it is characterized in that:The step 1 graphene/carbon nano-tube/Fe3O4Three-dimensional is multiple Closing the preparation of nano-particle is:It is 1 by mass ratio:1 acidifying carbon nanotubes and graphene oxide is dissolved in the first that mass ratio is 200 In alcohol, room temperature is stirred by ultrasonic to obtain black suspension;It is 0.224g/mL ferric chloride hexahydrates FeCl by concentration3·6H2O is dissolved in Deionized water, adds in above-mentioned black suspension, and it is four water of 0.165g/mL frerrous chlorides to add concentration after room temperature ultrasonic agitation Compound FeCl2·4H2O aqueous solution 20mL, room temperature add the ammonium hydroxide that mass ratio is 60 after being stirred by ultrasonic, room temperature is stirred by ultrasonic to obtain Black suspension;Above-mentioned suspension is centrifuged after the completion of reaction, takes lower sediment, is cleaned repeatedly with deionized water in being precipitated to Property, obtain graphene/carbon nano-tube/Fe3O4Three-dimensional composite nanoparticle.
- 7. according to the method described in claim 5, it is characterized in that:Solvent-free graphene/carbon nano-tube/the Fe of step 23O4 The preparation of three-dimensional composite Nano fluid is:Using silane coupling agent KH560 of the end containing epoxy group as neck-shaped layer, coronal layer uses For the oligomer polyetheramine M2070 with Amino End Group, both mass ratioes are 6.84:60,600mL methanol is dissolved in, magnetic force stirs Mix, when stirring 12-18 is small under the conditions of 45-60 DEG C, the upper Amino End Groups of M2070 form covalent bond with epoxy group on KH560, add stone Black alkene/carbon nanotubes/Fe3O4Three-dimensional composite nanoparticle, after the completion of stirring reaction, unreacted stone is removed with supercentrifuge Black alkene/carbon nanotubes/Fe3O4Three-dimensional composite nanoparticle, takes supernatant liquid dialysis drying to obtain black non transparent liquid, is Solvent-free graphene/carbon nano-tube/Fe3O4Three-dimensional composite Nano fluid.
- 8. according to the method described in claim 5, it is characterized in that:The solvent-free graphene/carbon nano-tube of the step 3/ Fe3O4The preparation of the epoxy resin nano composites of three-dimensional composite Nano fluid orientation enhancing:Using epoxy resin as matrix, The amine of ambient temperature curable adds 25~35 parts of amine curing agents and 0.1~3 as curing agent in 100 parts of epoxy resin Solvent-free graphene/carbon nano-tube/the Fe of part3O4Three-dimensional composite Nano fluid, ultrasound 0.3-0.5h, is placed on vacuum after stirring evenly Vacuumized in drying box, poured into after excluding bubble in ready mould, 0.5-1T magnetic fields are inserted in mould both sides, 70~80 After curing 24-30h at DEG C, solvent-free graphene/carbon nano-tube/Fe is obtained3O4The epoxy of three-dimensional composite Nano fluid orientation enhancing Nanocomposite.
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CN108949291A (en) * | 2018-07-09 | 2018-12-07 | 中国科学院兰州化学物理研究所 | The solvent-free graphene oxide-loaded silica nanometer class fluid of one kind and its application |
CN109163739A (en) * | 2018-08-20 | 2019-01-08 | 河南工业大学 | A method of preparing magneto-optic glass base single layer magnetic phasmon Terahertz sense film |
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CN110615972A (en) * | 2019-10-18 | 2019-12-27 | 北京航空航天大学 | Preparation method of high-toughness epoxy-graphene nanocomposite material with anti-abalone shell structure |
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101401542B1 (en) * | 2013-05-06 | 2014-06-03 | 한국기계연구원 | Electro-magnetic absorption film including graphene oxide, and the preparation method thereof |
CN104356600A (en) * | 2014-11-24 | 2015-02-18 | 嘉兴学院 | Carbon fiber composite material with high interlayer shearing performance and preparation method of carbon fiber composite material |
CN105733189A (en) * | 2016-03-06 | 2016-07-06 | 北京化工大学 | High-barrier composite material and preparation method based on two-dimensional nanofiller magnetic induced orientation |
CN106750517A (en) * | 2016-11-29 | 2017-05-31 | 陕西盛迈石油有限公司 | The preparation method of graphene oxide and epoxy resin composite material |
CN107140644A (en) * | 2017-06-15 | 2017-09-08 | 西北工业大学 | A kind of room temperature has the SiO of fluid behavior2Porous liquid and preparation method |
-
2017
- 2017-12-19 CN CN201711393342.4A patent/CN107987482A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
KR101401542B1 (en) * | 2013-05-06 | 2014-06-03 | 한국기계연구원 | Electro-magnetic absorption film including graphene oxide, and the preparation method thereof |
CN104356600A (en) * | 2014-11-24 | 2015-02-18 | 嘉兴学院 | Carbon fiber composite material with high interlayer shearing performance and preparation method of carbon fiber composite material |
CN105733189A (en) * | 2016-03-06 | 2016-07-06 | 北京化工大学 | High-barrier composite material and preparation method based on two-dimensional nanofiller magnetic induced orientation |
CN106750517A (en) * | 2016-11-29 | 2017-05-31 | 陕西盛迈石油有限公司 | The preparation method of graphene oxide and epoxy resin composite material |
CN107140644A (en) * | 2017-06-15 | 2017-09-08 | 西北工业大学 | A kind of room temperature has the SiO of fluid behavior2Porous liquid and preparation method |
Non-Patent Citations (4)
Title |
---|
HAIPENG BAI, YAPING ZHENG, RUILU YANG, AIBO ZHANG, NAN WANG: "Thermal and Mechanical Properties of Liquid-Like Trisilanol Isobutyl-Polyhedral Oligomeric Silsesquioxanes Derivative/Epoxy Nanocomposites", 《POLYMER COMPOSITES》 * |
PEIPEI LI, YAPING ZHENG, YIWEI WU, PING QU, RUILU YANG, MENGZHI: "Multifunctional Liquid-like Graphene@Fe3O4 Hybrid Nanofluid and Its Epoxy Nanocomposites", 《POLYMER COMPOSITES》 * |
史婷,郑亚萍,李沛沛: "不同沉积物无溶剂纳米石墨烯流体/环氧树脂复合材料阻燃性能对比", 《复合材料学报》 * |
邓富泉: "氧化石墨烯有序排列对碳纤维增强环氧树脂复合材料低温性能影响", 《高分子材料科学与工程》 * |
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