CN106566156A - Preparation method of graphene nanobelt/PMMA microcellular foam nanocomposite - Google Patents
Preparation method of graphene nanobelt/PMMA microcellular foam nanocomposite Download PDFInfo
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- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
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- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/044—Micropores, i.e. average diameter being between 0,1 micrometer and 0,1 millimeter
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- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
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- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
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Abstract
The invention relates to a preparation method of a graphene nanobelt/PMMA microcellular foam nanocomposite. The preparation method specifically comprises the following steps: spreading a multi-walled carbon nanotube through an oxidation method to obtain an oxidized graphene nanobelt, and then dispersing the oxidized graphene nanobelt in N, N-dimethylformamide (DMF) for high-temperature reflux and reduction, so as to obtain a graphene nanobelt dispersion liquid; after the graphene nanobelt dispersion liquid is blended with PMMA, carrying out ultrasonic dispersion, anti-solvent precipitation, freeze drying and hot-press molding treatment to obtain a graphene nanobelt/PMMA nanocomposite; then, putting the graphene nanobelt/PMMA nanocomposite into a high-pressure reaction kettle for supercritical carbon dioxide saturation; and after the saturation is finished, carrying out rapid pressure to obtain the graphene nanobelt/PMMA microcellular foam nanocomposite. The graphene nanobelt/PMMA microcellular foam nanocomposite obtained according to the preparation method provided by the invention is small in cell aperture, high in cell density and high in mechanical strength, and has broad application prospect in the fields of aerospace, electronic packaging, automotive protection and the like.
Description
Technical field
The present invention relates to a kind of preparation method of fretting map nano composite material, particularly a kind of graphene nanobelt/
The preparation method of PMMA fretting map nano composite materials.
Background technology
The scientists such as the Nam.P.Suh from the last century the eighties Massachusetts Institute of Technology propose microporous foam material for the first time
Since the concept of material, microcellular foam material with its unique foam structure, light weight it is high-strength, it is multi-functional the advantages of receive researcher
Extensive concern.In the preparation process of micro-foaming material, by adulterating in polymer matrix body, a small amount of nanoparticle can be with
The foaming condition of micro-foaming material is significantly reduced, and gives micro-foaming material unique performance, so as to expand out fretting map
Nano composite material.In the preparation process of fretting map nano composite material, due to the presence of nanoparticle, induction abscess into
Heterogeneous nucleating effect can be produced during core, nucleation barrier is greatly reduced, so as to obtain low abscess-size, high cell density
Fretting map nano composite material.Polymethyl methacrylate is a kind of important engineering plastics, with high intensity, it is corrosion-resistant,
Heat-insulated the advantages of, it is widely used in the fields such as automobile, packaging, building.Due to traditional pure PMMA micro-foaming materials abscess aperture
Larger, the low shortcoming of specific strength is subject to certain restrictions its application.
Grapheme material has excellent mechanics, electric property as a kind of novel nano-material, is now widely used for
The preparation of polymer nanocomposites.But the at present production in enormous quantities of high-quality graphene is still one to be limited it and extensively should
Topmost problem.The Graphene prepared by methods such as graphite oxides often has many defects, shadow in structure
Ring performance.Longitudinally launch multi-walled carbon nano-tubes to prepare graphene nanobelt by oxidizing process is a kind of new side for preparing Graphene
Method.Because current multi-walled carbon nano-tubes is commercially produced already and price is relatively low, therefore this method can also be produced in enormous quantities
Graphene nanobelt.It is little by the graphene nanobelt length-width ratio height of oxidizing process preparation, defect.Compare with CNT, graphite
Effective contact area between alkene nano belt and matrix is bigger, and bond strength is more preferable, so as to mechanical strength is higher.By in PMMA
Graphene nanobelt is introduced in matrix not only can improve the bubbling efficiency of PMMA micro-foaming materials, lower abscess aperture, improve
Cell density, while the mechanical strength and electric property of PMMA micro-foaming materials can also be improved.
Domestic and international patent is shown with document Investigation result：Not yet have at present and graphene nanobelt is introduced into PMMA matrix systems
The research report of standby fretting map nano composite material.
The content of the invention
It is an object of the invention to：For ordinary PMMA micro-foaming material cell density is little, the low shortcoming of mechanical strength,
The method that a kind of graphene nanobelt/PMMA fretting map nano composite materials are provided, the micro-foaming material that the method is prepared
Abscess-size is little, and cell density is high, excellent in mechanical performance, while operation is fairly simple, cost is relatively low, it is adaptable to which high-volume is raw
Produce.
The present invention solves its technical problem and employs the following technical solutions：
The preparation method of graphene nanobelt/PMMA fretting map nano composite materials that the present invention is provided, specifically：Pass through
Oxidizing process longitudinally launches multi-wall carbon nano-tube and is in control stannic oxide/graphene nano band, then stannic oxide/graphene nano band is dispersed in into N, N-
The backflow of dimethylformamide (DMF) high temperature carries out reduction and obtains graphene nanobelt dispersion liquid, the dispersion liquid and poly- methyl-prop
After e pioic acid methyl ester (PMMA) blending, Jing ultrasonic disperses, anti-solvent precipitation, lyophilization and hot-forming process obtain Graphene and receive
Rice band/PMMA nano composite materials, then the nano composite material is placed be placed in being carried out in autoclave in a mold
Supercritical carbon dioxide saturation, saturation finishes Jing quick pressure releasings and obtains graphene nanobelt/PMMA fretting map nano composite materials.
Described oxidizing process, specifically：By multi-walled carbon nano-tubes in dense H2SO4After middle stirring, a small amount of dense H is added3PO4, with
Potassium permanganate is added to react at 60-70 DEG C afterwards, potassium permanganate is 1 with the mass ratio of CNT:6, it is subsequently poured into and goes in a large number
Dilute in ionized water, then by H2O2Remaining potassium permanganate is removed with deionized water and wash to neutrality, it is last freeze-dried
Obtain stannic oxide/graphene nano band.
Described high temperature reflux, its technological parameter is：Reflux temperature is 150 DEG C, and return time is 4h.
Described PMMA, its mean molecule quantity is 100000-300000.
Described graphene nanobelt, it is with the mass percentage content of PMMA：0.1-5%.
Described graphene nanobelt, its dispersion concentration in DMF is 0.5-1.0mg/mL.
In said method, the mass ratio of PMMA and DMF is 1:10.
Described hot press forming technology is：Temperature 170-210 DEG C, pressure is 1-2MPa.
Described graphene nanobelt/saturation temperature of the PMMA nano composite materials in supercritical carbon dioxide is 60-
110 DEG C, saturation pressure is 12-18MPa, and saturation time is 8-12h.
Graphene nanobelt/PMMA fretting map nano composite materials prepared by the said method that the present invention is provided, it is in boat
Application in empty space flight, Electronic Packaging or automobile protective field.
The present invention has the advantages that compared with prior art following main：
1. there is preferable mechanical property and heat stability.
Graphene nanobelt/nano combined material of PMMA fretting maps compared with traditional preparation method, prepared by the present invention
Expect that (as little as 0.1wt.%) can realize relatively low abscess aperture (1～2 μm), and high abscess under relatively low graphene nanobelt doping
Density (～1011cells/cm3).Mechanics Performance Testing shows, and the pure PMMA fretting maps prepared under the conditions of same process
Material is compared, and its mechanical property can lift 10～80%.Saturation temperature be 80 DEG C, saturation pressure be 16MPa, saturation time
Under the conditions of for 8h, when the content of graphene nanobelt is 1.5wt.%, graphene nanobelt/PMMA (molecular weight is 100000)
The compressive strength of fretting map nano composite material is 21.6MPa, and the pure PMMA fretting maps prepared under the conditions of same process
The compressive strength of material is then 12MPa.Meanwhile, thermogravimetric analysiss test shows the maximum pyrolysis temperature of fretting map nano composite material
Also improve about 7 DEG C.As can be seen here graphene nanobelt can improve PMMA micro-foaming materials mechanical property and heat stability.
2. there is stronger operability and production application to be worth.
Using supercritical CO2Moulded from foam technology, process is simple, low cost, size is controllable, with stronger operability
With production application value.
Description of the drawings
Fig. 1-1 and Fig. 1-2 are respectively that multi-walled carbon nano-tubes is obtained with the stannic oxide/graphene nano band in preparation process with last
The XRD comparison diagrams and the transmission electron microscope picture of graphene nanobelt of the graphene nanobelt for arriving.
Fig. 2 is pure PMMA in 80 DEG C of saturation temperature, saturation pressure 16MPa, the microstructure of the abscess of saturation time 8h.
Fig. 3 is 0.1wt% graphene nanobelts/PMMA in 80 DEG C of saturation temperature, saturation pressure 16MPa, saturation time 8h
Abscess microstructure.
Fig. 4 is 0.5wt% graphene nanobelts/PMMA in 60 DEG C of saturation temperature, saturation pressure 18MPa, saturation time 8h
Abscess microstructure.
Fig. 5 is 1.0wt% graphene nanobelts/PMMA in 80 DEG C of saturation temperature, saturation pressure 16MPa, saturation time 8h
Abscess microstructure.
Fig. 6 is 5wt% graphene nanobelts/PMMA in 80 DEG C of saturation temperature, saturation pressure 12MPa, saturation time 8h's
The microstructure of abscess.
Fig. 7 is 1.0wt% graphene nanobelts/PMMA in 110 DEG C of saturation temperature, saturation pressure 16MPa, saturation time
The microstructure of the abscess of 12h.
Fig. 8 is 2.5wt% graphene nanobelts/PMMA in 85 DEG C of saturation temperature, saturation pressure 14MPa, saturation time 10h
Abscess microstructure.
Fig. 9 is the compressive strength test stress strain of the fretting map nano composite material of different graphene nanobelt contents
Figure.
Figure 10 is the heat stability of graphene nanobelt/PMMA fretting maps nano composite material and pure PMMA micro-foaming materials
Test chart.
Specific embodiment
The preparation method of graphene nanobelt/PMMA fretting map nano composite materials that the present invention is provided, first by height
Potassium manganate oxidation multi-wall carbon nano-tube tube in concentrated sulfuric acid solution prepares stannic oxide/graphene nano band, and stannic oxide/graphene nano band is existed
Solvothermal obtains graphene nanobelt in DMF solution.Then graphene nanobelt and PMMA matrixes are carried out into solution blending,
Graphene nanobelt/PMMA nano composite materials are obtained by the technique such as anti-solvent precipitation, lyophilization, hot-forming, finally
By supercritical CO2Fluid moulded from foam technology obtains graphene nanobelt/PMMA fretting map nano composite materials.
With reference to embodiment and accompanying drawing, the invention will be further described, but does not limit the present invention.
Embodiment 1：
Weigh 500mg multi-walled carbon nano-tubes to be put in beaker, add the H that 100mL mass concentrations are 98%2SO4, Jing magnetic force
Addition 10mL mass concentrations are 85% H in mixed liquor after stirring 1h3PO4, obtain carbon nanotube acid solution；
3g potassium permanganate is subsequently weighed, 1g potassium permanganate is added in carbon nanotube acid solution every 30min, continued holding and stir
Mix.Potassium permanganate is transferred to acid solution in there-necked flask after adding, heating in water bath 4h at 65 DEG C；After reaction is completed, by acid
Liquid pours 20%H containing 20ml into2O21L deionized waters in, stand 24h, obtain stannic oxide/graphene nano band acid solution.
Then stannic oxide/graphene nano band acid solution is washed to neutrality with a large amount of deionized waters, is aoxidized after lyophilization
Graphene nanobelt.By with the mass ratio of PMMA for 0.1-5% calculating and weigh stannic oxide/graphene nano band, by it in 100W
Into DMF solution, ultrasonic time 2h, dispersion liquid concentration is 0.5mg/mL to lower ultrasonic disperse.Dispersion liquid is transferred to into there-necked flask
In, heating in water bath at 150 DEG C, flow back 4h, obtains graphene nanobelt dispersion liquid.
Fig. 1-1 and Fig. 1-2 is stannic oxide/graphene nano band in multi-walled carbon nano-tubes and preparation process and finally obtain
The XRD comparison diagrams and the transmission electron microscope picture of graphene nanobelt of graphene nanobelt.Original multi-walled carbon nano-tubes diffraction maximum
Peak shape is sharp, and derivative peak occurs in 2 θ=25.8 °, and spacing of lattice is conversed for d=0.34nm by Bragg equation.Aoxidize it
Afterwards diffraction maximum occurs in 2 θ=11.6 °, and corresponding spacing of lattice is d=0.76nm, and spacing of lattice increases, and peak shape is gentle, table
Bright CNT has been obtained for launching, while many oxygen-containing functional groups of intercalation cause interlamellar spacing to increase.Heat is gone back in DMF solution
The diffraction maximum of the graphene nanobelt obtained after original occurs in 2 θ=25.4 °, and spacing of lattice is d=0.35nm, and close carbon is received
Mitron diffraction maximum, the oxygen-containing functional group for showing intercalation is removed, and has prepared graphene nanobelt.The graphite for finally obtaining
The transmission electron microscope picture of alkene nano belt shows that graphene nanobelt keeps banded structure, CNT to obtain longitudinal expansion, and
XRD results are consistent.
Embodiment 2：
Weigh 4g PMMA (relative molecular mass is 100000) to add in 40mL DMF solutions, the heated and stirred at 100 DEG C
30min so as to fully dissolving, is cooled to room temperature, obtains PMMA colloidal sols.Accurately weigh 0.0040g stannic oxide/graphene nanos band simultaneously
Graphene nanobelt dispersion liquid is prepared by the method in example 1.The PMMA colloidal sols for obtaining and graphene nanobelt are disperseed
Liquid mix homogeneously, ultrasound 4h, subsequent magnetic agitation 2h under 100W, obtains graphene nanobelt/PMMA dispersion liquids.Subsequently by stone
Black alkene nano belt/PMMA dispersion liquids are poured in 500mL dehydrated alcohol, precipitation, are filtered and with washing with alcohol 2-3 time, are obtained cotton-shaped
Thing.Floccule lyophilization 24h is removed into the DMF and ethanol of residual.Finally by the sample for obtaining hot pressing under 170 DEG C, 1MPa
Molding, obtains graphene nanobelt/PMMA nano composite materials.
The graphene nanobelt of above-mentioned preparation/PMMA nano composite materials are placed in 3mm moulds and are placed in reaction under high pressure
In kettle, saturation is carried out by supercritical carbon dioxide, saturation pressure is 16MPa, and saturation temperature is 80 DEG C, and saturation time is 8h,
Saturation conditions is opened fast decompression valve and is let out to normal pressure after completing, and is cooled down reactor with mixture of ice and water after 30s, finally
Obtain graphene nanobelt/PMMA fretting map nano composite materials.
The graphene nanobelt that the embodiment is obtained/PMMA fretting map nano composite materials, wherein graphene nanobelt
Content is 0.1wt%.Its foam structure as shown in figure 3, wherein mean cell diameter be 2.2m, average cell density be 9.5 ×
1010cells/cm3.Fig. 2 is the foam structure of pure PMMA micro-foaming materials under the conditions of same process, and wherein mean cell diameter is
20.1 μm, average cell density is 2.8 × 108cells/cm3.It can be seen that the abscess of graphene nanobelt/PMMA micro-foaming materials is close
Degree is apparently higher than pure PMMA micro-foaming materials under the same terms.
Embodiment 3：
Weigh 4g PMMA (relative molecular mass is 300000) to add in 40mLDMF solution, the heated and stirred at 100 DEG C
30min so as to fully dissolving, is cooled to room temperature, obtains PMMA colloidal sols.Accurately weigh 0.0201g stannic oxide/graphene nanos band simultaneously
Graphene nanobelt dispersion liquid is prepared by the method in example 1.The PMMA colloidal sols for obtaining and graphene nanobelt are disperseed
Liquid mix homogeneously, ultrasound 4h, subsequent magnetic agitation 2h under 100W, obtains graphene nanobelt/PMMA dispersion liquids.Subsequently by stone
Black alkene nano belt/PMMA dispersion liquids are poured in 500mL dehydrated alcohol, precipitation, are filtered and with washing with alcohol 2-3 time, are obtained cotton-shaped
Thing.Floccule lyophilization 24h is removed into the DMF and ethanol of residual.Finally by the sample for obtaining hot pressing under 210 DEG C, 2MPa
Molding, finally obtains graphene nanobelt/PMMA nano composite materials.
The graphene nanobelt of above-mentioned preparation/PMMA nano composite materials are placed in 3mm moulds and are placed in reaction under high pressure
In kettle, saturation is carried out by supercritical carbon dioxide, saturation pressure is 18MPa, and saturation temperature is 60 DEG C, and saturation time is 8h,
Saturation conditions is opened fast decompression valve and is let out to normal pressure after completing, and is cooled down reactor with mixture of ice and water after 30s, obtains
Graphene nanobelt/PMMA fretting map nano composite materials.
The graphene nanobelt that the embodiment is obtained/PMMA fretting map nano composite materials, wherein graphene nanobelt
Content is 0.5wt%.Its foam structure as shown in figure 4, mean cell diameter be 1.8 μm, average cell density be 1.9 ×
1011cells/cm3。
Embodiment 4：
Weigh 4g PMMA (relative molecular mass is 100000) to add in 40mL DMF solutions, the heated and stirred at 100 DEG C
30min so as to fully dissolving, is cooled to room temperature, obtains PMMA colloidal sols.Accurately weigh 0.0404g stannic oxide/graphene nanos band simultaneously
Graphene nanobelt dispersion liquid is prepared by the method in example 1.The PMMA colloidal sols for obtaining and graphene nanobelt are disperseed
Liquid mix homogeneously, ultrasound 4h, subsequent magnetic agitation 2h under 100W, obtains graphene nanobelt/PMMA dispersion liquids.Subsequently by stone
Black alkene nano belt/PMMA dispersion liquids are poured in 500mL dehydrated alcohol, precipitation, are filtered and with washing with alcohol 2-3 time, are obtained cotton-shaped
Thing.Floccule lyophilization 24h is removed into the DMF and ethanol of residual.Finally by the sample for obtaining hot pressing under 170 DEG C, 1MPa
Molding, finally obtains graphene nanobelt/PMMA nano composite materials.
The graphene nanobelt of above-mentioned preparation/PMMA nano composite materials are placed in 3mm moulds and are placed in reaction under high pressure
In kettle, saturation is carried out by supercritical carbon dioxide, saturation pressure is 16MPa, and saturation temperature is 80 DEG C, and saturation time is 8h,
Saturation conditions is opened fast decompression valve and is let out to normal pressure after completing, and is cooled down reactor with mixture of ice and water after 30s, obtains
Graphene nanobelt/PMMA fretting map nano composite materials.
The graphene nanobelt that the embodiment is obtained/PMMA fretting map nano composite materials, wherein graphene nanobelt
Content is 1.0wt%.Its foam structure as shown in figure 5, mean cell diameter be 1.5 μm, average cell density be 2.1 ×
1011cells/cm3。
Embodiment 5：
Weigh 4g PMMA (relative molecular mass is 100000) to add in 40mL DMF solutions, the heated and stirred at 100 DEG C
30min so as to fully dissolving, is cooled to room temperature, obtains PMMA colloidal sols.Accurately weigh 0.2105g stannic oxide/graphene nanos band simultaneously
Graphene nanobelt dispersion liquid is prepared by the method in example 1.The PMMA colloidal sols for obtaining and graphene nanobelt are disperseed
Liquid mix homogeneously, ultrasound 4h, subsequent magnetic agitation 2h under 100W, obtains graphene nanobelt/PMMA dispersion liquids.Subsequently by stone
Black alkene nano belt/PMMA dispersion liquids are poured in 500mL dehydrated alcohol, precipitation, are filtered and with washing with alcohol 2-3 time, are obtained cotton-shaped
Thing.Floccule lyophilization 24h is removed into the DMF and ethanol of residual.Floccule lyophilization 24h is removed into solvent, has been dried
Entirely.It is finally that the sample for obtaining is hot-forming under 170 DEG C, 1MPa, finally obtain the nano combined materials of graphene nanobelt/PMMA
Material.
The graphene nanobelt of above-mentioned preparation/PMMA nano composite materials are placed in 3mm moulds and are placed in reaction under high pressure
In kettle, saturation is carried out by supercritical carbon dioxide, saturation pressure is 12MPa, and saturation temperature is 80 DEG C, and saturation time is 8h,
Saturation conditions is opened fast decompression valve and is let out to normal pressure after completing, and is cooled down reactor with mixture of ice and water after 30s, obtains
Graphene nanobelt/PMMA fretting map nano composite materials.
The graphene nanobelt that the embodiment is obtained/PMMA fretting map nano composite materials, wherein graphene nanobelt
Content is 5wt%.Its foam structure as shown in fig. 6, mean cell diameter be 1.3 μm, average cell density be 3.1 ×
1011cells/cm3。
Embodiment 6：
Weigh 4g PMMA (relative molecular mass is 100000) to add in 40mL DMF solutions, the heated and stirred at 100 DEG C
30min so as to fully dissolving, is cooled to room temperature, obtains PMMA colloidal sols.Accurately weigh 0.0404g stannic oxide/graphene nanos band simultaneously
Graphene nanobelt dispersion liquid is prepared by the method in example 1.The PMMA colloidal sols for obtaining and graphene nanobelt are disperseed
Liquid mix homogeneously, ultrasound 4h, subsequent magnetic agitation 2h under 100W, obtains graphene nanobelt/PMMA dispersion liquids.Subsequently by stone
Black alkene nano belt/PMMA dispersion liquids are poured in 500mL dehydrated alcohol, precipitation, are filtered and with washing with alcohol 2-3 time, are obtained cotton-shaped
Thing.Floccule lyophilization 24h is removed into the DMF and ethanol of residual.Floccule lyophilization 24h is removed into solvent, has been dried
Entirely.It is finally that the sample for obtaining is hot-forming under 170 DEG C, 1MPa, finally obtain the nano combined materials of graphene nanobelt/PMMA
Material.
The graphene nanobelt of above-mentioned preparation/PMMA nano composite materials are placed in 3mm moulds and are placed in reaction under high pressure
In kettle, saturation is carried out by supercritical carbon dioxide, saturation pressure is 16MPa, and saturation temperature is 110 DEG C, and saturation time is
12h, saturation conditions is opened fast decompression valve and is let out to normal pressure after completing, and is cooled down reactor with mixture of ice and water after 30s,
Obtain graphene nanobelt/PMMA fretting map nano composite materials.
The 1.0wt% graphene nanobelts that the embodiment is obtained/PMMA fretting map nano composite materials, it is in saturation temperature
Micro-foaming material at 110 DEG C.Its foam structure as shown in fig. 7, mean cell diameter be 9.3 μm, average cell density is 2.1
×109cells/cm3。
Embodiment 7：
Weigh 4g PMMA (relative molecular mass is 100000) to add in 40mLDMF solution, the heated and stirred at 100 DEG C
30min so as to fully dissolving, is cooled to room temperature, obtains PMMA colloidal sols.Accurately weigh 0.1026g stannic oxide/graphene nanos band simultaneously
Graphene nanobelt dispersion liquid is prepared by the method in example 1.The PMMA colloidal sols for obtaining and graphene nanobelt are disperseed
Liquid mix homogeneously, ultrasound 4h, subsequent magnetic agitation 2h under 100W, obtains graphene nanobelt/PMMA dispersion liquids.Subsequently by stone
Black alkene nano belt/PMMA dispersion liquids are poured in 500mL dehydrated alcohol, precipitation, are filtered and with washing with alcohol 2-3 time, are obtained cotton-shaped
Thing.Floccule lyophilization 24h is removed into the DMF and ethanol of residual.Floccule lyophilization 24h is removed into solvent, has been dried
Entirely.It is finally that the sample for obtaining is hot-forming under 170 DEG C, 1MPa, finally obtain the nano combined materials of graphene nanobelt/PMMA
Material.
The graphene nanobelt of above-mentioned preparation/PMMA nano composite materials are placed in 3mm moulds and are placed in reaction under high pressure
In kettle, saturation is carried out by supercritical carbon dioxide, saturation pressure is 14MPa, and saturation temperature is 85 DEG C, and saturation time is 10h,
Saturation conditions is opened fast decompression valve and is let out to normal pressure after completing, and is cooled down reactor with mixture of ice and water after 30s, obtains
Graphene nanobelt/PMMA fretting map nano composite materials.
The 2.5wt% graphene nanobelts that the embodiment is obtained/PMMA fretting map nano composite materials, it is in saturation temperature
Micro-foaming material at 85 DEG C.Its foam structure as shown in figure 9, mean cell diameter be 1.4 μm, average cell density is 2.5
×109cells/cm3。
Graphene nanobelt/PMMA fretting maps nano composite material has higher mechanical property than pure PMMA micro-foaming materials
Energy (under the conditions of same process, as shown in Figure 9) and higher heat stability (as shown in Figure 10).
Claims (10)
1. the preparation method of graphene nanobelt/PMMA fretting map nano composite materials, is characterized in that by oxidizing process longitudinal direction exhibition
Open multi-wall carbon nano-tube and be in control stannic oxide/graphene nano band, then stannic oxide/graphene nano band is dispersed in into DMF high temperatures and flow back into
Row reduction obtains graphene nanobelt dispersion liquid, after the dispersion liquid is blended with PMMA, Jing ultrasonic disperses, anti-solvent precipitation, freezing
Dry and hot-forming process obtains graphene nanobelt/PMMA nano composite materials, then places the nano composite material
It is placed in a mold carrying out supercritical carbon dioxide saturation in autoclave, saturation finishes Jing quick pressure releasings and obtains Graphene
Nano belt/PMMA fretting map nano composite materials.
2. preparation method according to claim 1, it is characterised in that described oxidizing process, specifically：By multi-wall carbon nano-tube
Guan Nong H2SO4After middle stirring, a small amount of dense H is added3PO4, be subsequently added potassium permanganate and react at 60-70 DEG C, potassium permanganate with
The mass ratio of CNT is 1:6, it is subsequently poured in a large amount of deionized waters and dilutes, then by H2O2Remove with deionized water remaining
Potassium permanganate and wash to neutrality, it is last freeze-dried to obtain stannic oxide/graphene nano band.
3. preparation method according to claim 1, it is characterised in that described high temperature reflux, its technological parameter is：Backflow
Temperature is 150 DEG C, and return time is 4h.
4. preparation method according to claim 1, it is characterised in that PMMA mean molecule quantities are 100000-300000.
5. preparation method according to claim 1, it is characterised in that described graphene nanobelt, its quality with PMMA
Degree is：0.1-5%.
6. preparation method according to claim 1, it is characterised in that described graphene nanobelt, its in DMF point
Scattered concentration is 0.5-1.0mg/mL.
7. preparation method according to claim 1, it is characterised in that the mass ratio of PMMA and DMF is 1:10.
8. preparation method according to claim 1, it is characterised in that described hot press forming technology is：Temperature 170-210
DEG C, pressure is 1-2MPa.
9. preparation method according to claim 1, it is characterised in that the described nano combined materials of graphene nanobelt/PMMA
Saturation temperature of the material in supercritical carbon dioxide is 60-110 DEG C, and saturation pressure is 12-18MPa, and saturation time is 8-12h.
10. graphene nanobelt/PMMA fretting map nano composite materials that in claim 1 to 9 prepared by arbitrary methods described, its
It is characterized in that application of the nano composite material in Aero-Space, Electronic Packaging or automobile protective field.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107163173A (en) * | 2017-05-12 | 2017-09-15 | 陕西理工大学 | A kind of preparation method of amorphous polymer fretting map plate |
| CN107365470A (en) * | 2017-06-29 | 2017-11-21 | 上海金山锦湖日丽塑料有限公司 | A kind of high heat-resisting HI high impact PMMA resins and preparation method thereof |
| CN108927202A (en) * | 2018-09-25 | 2018-12-04 | 岭南师范学院 | A kind of g-C3N4Nanobelt and the preparation method and application thereof |
| EP3660083A1 (en) * | 2018-11-30 | 2020-06-03 | SABIC Global Technologies B.V. | Polymer foams including functionalized carbon nanotubes |
| CN113788474A (en) * | 2021-11-04 | 2021-12-14 | 航天特种材料及工艺技术研究所 | Graphene nanoribbon horizontal array and preparation method and application thereof |
| CN114953493A (en) * | 2022-06-06 | 2022-08-30 | 浙江新恒泰新材料有限公司 | Supercritical foaming composite material preparation equipment and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103302861A (en) * | 2013-05-16 | 2013-09-18 | 武汉理工大学 | Preparation method of polymethyl methacrylate based cell gradient material |
-
2016
- 2016-11-02 CN CN201610943930.XA patent/CN106566156B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103302861A (en) * | 2013-05-16 | 2013-09-18 | 武汉理工大学 | Preparation method of polymethyl methacrylate based cell gradient material |
Non-Patent Citations (5)
| Title |
|---|
| HAO-BIN ZHANG 等: "Tough Graphene-Polymer Microcellular Foams for Electromagnetic Interference Shielding", 《ACS APPL. MATER. INTERFACES》 * |
| MEIJUAN LI 等: "Preparation of PMMA/graphene oxide microcellular foams using supercritical carbon dioxide", 《IOP CONFERENCE SERIES: MATERIALS SCIENCE AND ENGINEERING》 * |
| MOHAMMAD A 等: "Graphene Nanoribbon Composites", 《ACS NANO》 * |
| XIANG-FENG WU 等: "Preparation of Reduced-Graphene Nanoribbons via One-Step Solvothermal Process", 《J. NANOSCI. NANOTECHNOL.》 * |
| YUAN HUAN 等: "Microstructure and Electrical Conductivity of CNTs/PMMA Nanocomposite Foams Foaming by Supercritical Carbon Dioxide", 《JOURNAL OF WUHAN UNIVERSITY OF TECHNOLOGY-MATER. SCI. ED.》 * |
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|---|---|---|---|---|
| CN107163173A (en) * | 2017-05-12 | 2017-09-15 | 陕西理工大学 | A kind of preparation method of amorphous polymer fretting map plate |
| CN107163173B (en) * | 2017-05-12 | 2019-03-12 | 陕西理工大学 | A kind of preparation method of amorphous polymer fretting map plate |
| CN107365470A (en) * | 2017-06-29 | 2017-11-21 | 上海金山锦湖日丽塑料有限公司 | A kind of high heat-resisting HI high impact PMMA resins and preparation method thereof |
| CN107365470B (en) * | 2017-06-29 | 2019-09-17 | 上海金山锦湖日丽塑料有限公司 | A kind of high heat resistance HI high impact PMMA resin and preparation method thereof |
| CN108927202A (en) * | 2018-09-25 | 2018-12-04 | 岭南师范学院 | A kind of g-C3N4Nanobelt and the preparation method and application thereof |
| CN108927202B (en) * | 2018-09-25 | 2021-05-07 | 岭南师范学院 | g-C3N4Nanobelt and preparation method and application thereof |
| EP3660083A1 (en) * | 2018-11-30 | 2020-06-03 | SABIC Global Technologies B.V. | Polymer foams including functionalized carbon nanotubes |
| WO2020110052A1 (en) * | 2018-11-30 | 2020-06-04 | Sabic Global Technologies B.V. | Polymer foams including functionalized carbon nanotubes |
| CN113788474A (en) * | 2021-11-04 | 2021-12-14 | 航天特种材料及工艺技术研究所 | Graphene nanoribbon horizontal array and preparation method and application thereof |
| CN114953493A (en) * | 2022-06-06 | 2022-08-30 | 浙江新恒泰新材料有限公司 | Supercritical foaming composite material preparation equipment and preparation method thereof |
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