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 PDF

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CN107987482A
CN107987482A CN201711393342.4A CN201711393342A CN107987482A CN 107987482 A CN107987482 A CN 107987482A CN 201711393342 A CN201711393342 A CN 201711393342A CN 107987482 A CN107987482 A CN 107987482A
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graphene
tube
nano
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dimensional composite
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郑亚萍
彭宁昆
王田宇
王钰登
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Northwestern Polytechnical University
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K3/04Carbon
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08K7/24Expanded, porous or hollow particles inorganic
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    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C09K5/00Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/08Materials not undergoing a change of physical state when used
    • C09K5/14Solid materials, e.g. powdery or granular
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00Specific properties of additives
    • C08K2201/011Nanostructured additives

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

Solvent-free graphene/carbon nano-tube/ferroso-ferric oxide three-dimensional composite Nano fluid epoxy Resin and preparation method
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)

  1. 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. 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. 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. 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. 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. 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. 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. 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.
CN201711393342.4A 2017-12-19 2017-12-19 Solvent-free graphene/carbon nano-tube/ferroso-ferric oxide three-dimensional composite Nano fluid epoxy resin and preparation method Pending CN107987482A (en)

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Cited By (10)

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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
CN109763184A (en) * 2018-12-18 2019-05-17 重庆中科烯维科技有限公司 A kind of production method of the magnetic oxygenated graphene-carbon nano tube conductive fiber of orientationization
CN110451893A (en) * 2019-08-28 2019-11-15 成都理工大学 A kind of development of cement base electromagnetism composite material, preparation method and applications
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
CN110669315A (en) * 2019-10-08 2020-01-10 西北工业大学 Preparation method of hybrid nano paper/EP/CF wave-absorbing composite material
CN111303813A (en) * 2020-04-22 2020-06-19 中国工程物理研究院电子工程研究所 Room temperature curing pouring sealant for precise electronic components and use method thereof
CN112063200A (en) * 2020-09-06 2020-12-11 西北工业大学 MXene-based solvent-free nano fluid and preparation method thereof
CN112522951A (en) * 2020-12-08 2021-03-19 长春工业大学 Graphene oxide/ferroferric oxide nanofluid modified water-based epoxy sizing agent, carbon fiber epoxy composite material and preparation method
CN114163778A (en) * 2021-09-17 2022-03-11 兰州交通大学 Solvent-free nano fluid-filled epoxy resin-based self-lubricating composite material

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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
CN108949291B (en) * 2018-07-09 2021-05-25 中国科学院兰州化学物理研究所 Solvent-free graphene oxide loaded silicon dioxide nano fluid and application thereof
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
CN109763184A (en) * 2018-12-18 2019-05-17 重庆中科烯维科技有限公司 A kind of production method of the magnetic oxygenated graphene-carbon nano tube conductive fiber of orientationization
CN110451893A (en) * 2019-08-28 2019-11-15 成都理工大学 A kind of development of cement base electromagnetism composite material, preparation method and applications
CN110451893B (en) * 2019-08-28 2022-04-15 成都理工大学 Cement-based electromagnetic development composite material, preparation method and application thereof
CN110669315B (en) * 2019-10-08 2022-04-22 西北工业大学 Preparation method of hybrid nano paper/EP/CF wave-absorbing composite material
CN110669315A (en) * 2019-10-08 2020-01-10 西北工业大学 Preparation method of hybrid nano paper/EP/CF wave-absorbing composite material
CN110615972B (en) * 2019-10-18 2021-01-22 北京航空航天大学 Preparation method of high-toughness epoxy-graphene nanocomposite material with anti-abalone shell structure
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
CN111303813B (en) * 2020-04-22 2022-02-18 中国工程物理研究院电子工程研究所 Room temperature curing pouring sealant for precise electronic components and use method thereof
CN111303813A (en) * 2020-04-22 2020-06-19 中国工程物理研究院电子工程研究所 Room temperature curing pouring sealant for precise electronic components and use method thereof
CN112063200A (en) * 2020-09-06 2020-12-11 西北工业大学 MXene-based solvent-free nano fluid and preparation method thereof
CN112522951A (en) * 2020-12-08 2021-03-19 长春工业大学 Graphene oxide/ferroferric oxide nanofluid modified water-based epoxy sizing agent, carbon fiber epoxy composite material and preparation method
CN112522951B (en) * 2020-12-08 2023-02-28 长春工业大学 Graphene oxide/ferroferric oxide nanofluid modified water-based epoxy sizing agent, carbon fiber epoxy composite material and preparation method
CN114163778A (en) * 2021-09-17 2022-03-11 兰州交通大学 Solvent-free nano fluid-filled epoxy resin-based self-lubricating composite material

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