CN106566156B - The preparation method of graphene nanobelt/PMMA fretting map nanocomposites - Google Patents
The preparation method of graphene nanobelt/PMMA fretting map nanocomposites Download PDFInfo
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- 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
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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
- C08J2333/04—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
- 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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- C08K2201/011—Nanostructured additives
Abstract
The present invention relates to a kind of preparation methods of graphene nanobelt/PMMA fretting map nanocomposites, specifically：By oxidizing process, longitudinally expansion multi-wall carbon nano-tube is in control stannic oxide/graphene nano band, stannic oxide/graphene nano band is dispersed in N again, the reflux of N dimethylformamides (DMF) high temperature is restored to obtain graphene nanobelt dispersion liquid, after the dispersion liquid is blended with PMMA, through ultrasonic disperse, anti-solvent precipitates, freeze-drying and hot-forming processing obtain graphene nanobelt/PMMA nanocomposites, then nanocomposite placement is placed in progress supercritical carbon dioxide saturation in autoclave in a mold, saturation is finished obtains graphene nanobelt/PMMA fretting map nanocomposites through quick pressure releasing.Micro-foaming material abscess aperture prepared by the present invention is small, and cell density is high, and mechanical strength is big, is with a wide range of applications in fields such as aerospace, Electronic Packaging, automobile protectives.
Description
Technical field
The present invention relates to a kind of preparation method of fretting map nanocomposite, especially a kind of graphene nanobelt/
The preparation method of PMMA fretting map nanocomposites.
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, it is light high-strength, multi-functional the advantages that receive researcher
Extensive concern.It, can be with by adulterating a small amount of nano-particle in polymer matrix body in the preparation process of micro-foaming material
The foaming condition of micro-foaming material is significantly reduced, and assigns micro-foaming material unique performance, the fretting map to expand out
Nanocomposite.In the preparation process of fretting map nanocomposite, due to the presence of nano-particle, induction abscess at
It will produce heterogeneous nucleating effect during core, greatly reduce nucleation barrier, to obtain low abscess-size, high cell density
Fretting map nanocomposite.Polymethyl methacrylate is a kind of important engineering plastics, have high intensity, it is corrosion-resistant,
The advantages that heat-insulated, is widely used in the fields such as automobile, packaging, building.Due to traditional pure PMMA micro-foaming materials abscess aperture
Larger, the disadvantages such as specific strength is low make its application be subject to certain restrictions.
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 mass production of high-quality graphene at present is still one and limits it and answer extensively
Most important problem.The graphene being prepared by the methods of graphite oxide often has many defects, shadow in structure
Ring performance.It is a kind of new side preparing graphene that by oxidizing process, longitudinally expansion multi-walled carbon nanotube, which prepares graphene nanobelt,
Method.Since current multi-walled carbon nanotube is commercially produced and price is relatively low already, this method can also be produced in enormous quantities
Graphene nanobelt.It is small by the graphene nanobelt length-width ratio height of oxidizing process preparation, defect.It is compared with carbon nanotube, graphite
Effective contact area bigger between alkene nanobelt and matrix, bond strength is more preferable, to mechanical strength higher.By in PMMA
Graphene nanobelt is introduced in matrix can not only 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.
To domestic and international patent and document Investigation the result shows that：There has been no graphene nanobelt is introduced PMMA matrix systems at present
The research report of standby fretting map nanocomposite.
Invention content
It is an object of the invention to：For ordinary PMMA micro-foaming material cell density is small, the disadvantages such as mechanical strength is low,
A kind of method of graphene nanobelt/PMMA fretting map nanocomposites, the micro-foaming material that this method is prepared are provided
Abscess-size is small, and cell density is high, excellent in mechanical performance, while operating fairly simple, and cost is relatively low, and it is raw to be suitable for high-volume
Production.
The present invention solves its technical problem and uses following technical scheme：
The preparation method of graphene nanobelt provided by the invention/PMMA fretting map nanocomposites, specifically：Pass through
Longitudinally expansion multi-wall carbon nano-tube is in control stannic oxide/graphene nano band to oxidizing process, then stannic oxide/graphene nano band is dispersed in N, N-
The reflux of dimethylformamide (DMF) high temperature is restored to obtain graphene nanobelt dispersion liquid, the dispersion liquid and poly- methyl-prop
After e pioic acid methyl ester (PMMA) is blended, obtains graphene through ultrasonic disperse, anti-solvent precipitation, freeze-drying and hot-forming processing and receive
Then nanocomposite placement is placed in autoclave and carries out by rice band/PMMA nanocomposites in a mold
Supercritical carbon dioxide is saturated, and saturation is finished obtains graphene nanobelt/PMMA fretting map nanocomposites through quick pressure releasing.
The oxidizing process, specifically：By multi-walled carbon nanotube in dense H2SO4After middle stirring, a small amount of dense H is added3PO4, with
Potassium permanganate is added afterwards to react at 60-70 DEG C, the mass ratio of potassium permanganate and carbon nanotube is 1:6, it is subsequently poured into and largely goes
It is diluted in ionized water, then passes through H2O2Remaining potassium permanganate is removed with deionized water and is washed to neutrality, it is last freeze-dried
Obtain stannic oxide/graphene nano band.
The high temperature reflux, technological parameter are：Reflux temperature is 150 DEG C, return time 4h.
The PMMA, average molecular weight 100000-300000.
The graphene nanobelt, the mass percentage content with PMMA are：0.1-5%.
The graphene nanobelt, the dispersion concentration in DMF are 0.5-1.0mg/mL.
In the above method, the mass ratio of PMMA and DMF are 1:10.
The hot press forming technology is：170-210 DEG C of temperature, pressure 1-2MPa.
The graphene nanobelt/saturation temperature of the PMMA nanocomposites in supercritical carbon dioxide is 60-
110 DEG C, saturation pressure 12-18MPa, saturation time 8-12h.
Graphene nanobelt/PMMA fretting map nanocomposites prepared by the above method provided by the invention, are navigating
Application in empty space flight, Electronic Packaging or automobile protective field.
The present invention has the advantages that following main compared with prior art：
1. having preferable mechanical property and thermal stability.
Compared with traditional preparation method, graphene nanobelt/nano combined material of PMMA fretting maps prepared by the present invention
Material can realize relatively low abscess aperture (1~2 μm) and high abscess (down to 0.1wt.%) under the doping of lower graphene nanobelt
Density (~1011cells/cm3).Mechanics Performance Testing show and same process under the conditions of the pure PMMA fretting maps that are prepared
Material is compared, and mechanical property can promote 10~80%.Saturation temperature be 80 DEG C, saturation pressure 16MPa, saturation time
Under the conditions of 8h, when the content of graphene nanobelt is 1.5wt.%, graphene nanobelt/PMMA (molecular weight 100000)
The compressive strength of fretting map nanocomposite is 21.6MPa, and the pure PMMA fretting maps being prepared under the conditions of same process
The compressive strength of material is then 12MPa.Meanwhile thermogravimetric analysis test shows the maximum pyrolysis temperature of fretting map nanocomposite
Also improve about 7 DEG C.It can be seen that graphene nanobelt can improve PMMA micro-foaming materials mechanical property and thermal stability.
2. being worth with stronger operability and production application.
Using supercritical CO2Moulded from foam technology, simple process and low cost, size is controllable, has stronger operability
It is worth with production application.
Description of the drawings
Fig. 1-1 and Fig. 1-2 is that multi-walled carbon nanotube is obtained with the stannic oxide/graphene nano band in preparation process with last respectively
The XRD comparison diagrams of the graphene nanobelt arrived and the transmission electron microscope picture of graphene nanobelt.
Fig. 2 is pure PMMA in 80 DEG C, saturation pressure 16MPa of saturation temperature, the microstructure of the abscess of saturation time 8h.
Fig. 3 is 0.1wt% graphene nanobelts/PMMA in 80 DEG C, saturation pressure 16MPa, saturation time 8h of saturation temperature
Abscess microstructure.
Fig. 4 is 0.5wt% graphene nanobelts/PMMA in 60 DEG C, saturation pressure 18MPa, saturation time 8h of saturation temperature
Abscess microstructure.
Fig. 5 is 1.0wt% graphene nanobelts/PMMA in 80 DEG C, saturation pressure 16MPa, saturation time 8h of saturation temperature
Abscess microstructure.
Fig. 6 is 5wt% graphene nanobelts/PMMA in 80 DEG C, saturation pressure 12MPa of saturation temperature, saturation time 8h's
The microstructure of abscess.
Fig. 7 is 1.0wt% graphene nanobelts/PMMA in 110 DEG C, saturation pressure 16MPa of saturation temperature, saturation time
The microstructure of the abscess of 12h.
Fig. 8 is 2.5wt% graphene nanobelts/PMMA in 85 DEG C, saturation pressure 14MPa, saturation time 10h of saturation temperature
Abscess microstructure.
Fig. 9 is the compressive strength test stress strain of the fretting map nanocomposite of different graphene nanobelt contents
Figure.
Figure 10 is the thermal stability of graphene nanobelt/PMMA fretting maps nanocomposite and pure PMMA micro-foaming materials
Test chart.
Specific implementation mode
The preparation method of graphene nanobelt provided by the invention/PMMA fretting map nanocomposites, passes through height first
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 subjected to solution blending,
Graphene nanobelt/PMMA nanocomposites are obtained by the techniques such as anti-solvent precipitation, freeze-drying, hot-forming, finally
Pass through supercritical CO2Fluid moulded from foam technology obtains graphene nanobelt/PMMA fretting map nanocomposites.
With reference to embodiment and attached drawing, the invention will be further described, but does not limit the present invention.
Embodiment 1：
It weighs 500mg multi-walled carbon nanotubes to be put into beaker, the H that 100mL mass concentrations are 98% is added2SO4, through magnetic force
The H that 10mL mass concentrations are 85% is added into mixed liquor after stirring 1h3PO4, obtain carbon nanotube acid solution；
3g potassium permanganate then is weighed, 1g potassium permanganate is added into carbon nanotube acid solution every 30min, continues to keep stirring
It mixes.Acid solution is transferred in three-necked flask by potassium permanganate after adding, heating water bath 4h at 65 DEG C；It, will be sour after reaction is completed
Liquid pours into 20%H containing 20ml2O21L deionized waters in, stand for 24 hours, 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 freeze-drying
Graphene nanobelt.Stannic oxide/graphene nano band is calculated and weighs for 0.1-5%, by the mass ratio with PMMA by it in 100W
In lower ultrasonic disperse to DMF solution, ultrasonic time 2h, dispersion liquid concentration 0.5mg/mL.Dispersion liquid is transferred to three-necked flask
In, heating 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 nanotube and preparation process and finally obtains
The XRD comparison diagrams of graphene nanobelt and the transmission electron microscope picture of graphene nanobelt.Original multi-walled carbon nanotube diffraction maximum
Peak shape is sharp, and derivative peak appears in 2 θ=25.8 °, and it is d=0.34nm to converse spacing of lattice by Bragg equation.Aoxidize it
Diffraction maximum appears in 2 θ=11.6 ° afterwards, and corresponding spacing of lattice is d=0.76nm, and spacing of lattice increases, and peak shape is gentle, table
Bright carbon nanotube has been obtained for being unfolded, while many oxygen-containing functional groups of intercalation make interlamellar spacing increase.Heat is gone back in DMF solution
The diffraction maximum of the graphene nanobelt obtained after former appears in 2 θ=25.4 °, and spacing of lattice d=0.35nm receives close to carbon
Mitron diffraction maximum shows that the oxygen-containing functional group of intercalation is removed, graphene nanobelt has been prepared.The graphite finally obtained
The transmission electron microscope picture of alkene nanobelt shows that graphene nanobelt keeps banded structure, carbon nanotube to obtain longitudinal expansion, and
XRD results are consistent.
Embodiment 2：
It weighs 4g PMMA (relative molecular mass 100000) to be added in 40mL DMF solutions, the heating stirring at 100 DEG C
30min makes it fully dissolve, and is cooled to room temperature, and 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.Obtained PMMA colloidal sols and graphene nanobelt are disperseed
Liquid is uniformly mixed, and the ultrasound 4h at 100W, subsequent magnetic agitation 2h obtain graphene nanobelt/PMMA dispersion liquids.Then by stone
Black alkene nanobelt/PMMA dispersion liquids pour into 500mL absolute ethyl alcohols, and precipitation is filtered and washed 2-3 times with ethyl alcohol, is obtained cotton-shaped
Object.Floccule freeze-drying is removed into remaining DMF and ethyl alcohol for 24 hours.Finally by the hot pressing at 170 DEG C, 1MPa of obtained sample
Molding, obtains graphene nanobelt/PMMA nanocomposites.
The graphene nanobelt of above-mentioned preparation/PMMA nanocomposites are placed in 3mm molds and are placed in reaction under high pressure
It in kettle, being saturated by supercritical carbon dioxide, saturation pressure 16MPa, saturation temperature is 80 DEG C, saturation time 8h,
Saturation conditions is opened fast decompression valve after completing and is let out to normal pressure, is cooled down reaction kettle with mixture of ice and water after 30s, finally
Obtain graphene nanobelt/PMMA fretting map nanocomposites.
The graphene nanobelt that the embodiment obtains/PMMA fretting map nanocomposites, 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：
It weighs 4g PMMA (relative molecular mass 300000) to be added in 40mLDMF solution, the heating stirring at 100 DEG C
30min makes it fully dissolve, and is cooled to room temperature, and 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.Obtained PMMA colloidal sols and graphene nanobelt are disperseed
Liquid is uniformly mixed, and the ultrasound 4h at 100W, subsequent magnetic agitation 2h obtain graphene nanobelt/PMMA dispersion liquids.Then by stone
Black alkene nanobelt/PMMA dispersion liquids pour into 500mL absolute ethyl alcohols, and precipitation is filtered and washed 2-3 times with ethyl alcohol, is obtained cotton-shaped
Object.Floccule freeze-drying is removed into remaining DMF and ethyl alcohol for 24 hours.Finally by the hot pressing at 210 DEG C, 2MPa of obtained sample
Molding, finally obtains graphene nanobelt/PMMA nanocomposites.
The graphene nanobelt of above-mentioned preparation/PMMA nanocomposites are placed in 3mm molds and are placed in reaction under high pressure
It in kettle, being saturated by supercritical carbon dioxide, saturation pressure 18MPa, saturation temperature is 60 DEG C, saturation time 8h,
Saturation conditions is opened fast decompression valve after completing and is let out to normal pressure, cools down reaction kettle with mixture of ice and water after 30s, obtains
Graphene nanobelt/PMMA fretting map nanocomposites.
The graphene nanobelt that the embodiment obtains/PMMA fretting map nanocomposites, 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：
It weighs 4g PMMA (relative molecular mass 100000) to be added in 40mL DMF solutions, the heating stirring at 100 DEG C
30min makes it fully dissolve, and is cooled to room temperature, and 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.Obtained PMMA colloidal sols and graphene nanobelt are disperseed
Liquid is uniformly mixed, and the ultrasound 4h at 100W, subsequent magnetic agitation 2h obtain graphene nanobelt/PMMA dispersion liquids.Then by stone
Black alkene nanobelt/PMMA dispersion liquids pour into 500mL absolute ethyl alcohols, and precipitation is filtered and washed 2-3 times with ethyl alcohol, is obtained cotton-shaped
Object.Floccule freeze-drying is removed into remaining DMF and ethyl alcohol for 24 hours.Finally by the hot pressing at 170 DEG C, 1MPa of obtained sample
Molding, finally obtains graphene nanobelt/PMMA nanocomposites.
The graphene nanobelt of above-mentioned preparation/PMMA nanocomposites are placed in 3mm molds and are placed in reaction under high pressure
It in kettle, being saturated by supercritical carbon dioxide, saturation pressure 16MPa, saturation temperature is 80 DEG C, saturation time 8h,
Saturation conditions is opened fast decompression valve after completing and is let out to normal pressure, cools down reaction kettle with mixture of ice and water after 30s, obtains
Graphene nanobelt/PMMA fretting map nanocomposites.
The graphene nanobelt that the embodiment obtains/PMMA fretting map nanocomposites, 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：
It weighs 4g PMMA (relative molecular mass 100000) to be added in 40mL DMF solutions, the heating stirring at 100 DEG C
30min makes it fully dissolve, and is cooled to room temperature, and 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.Obtained PMMA colloidal sols and graphene nanobelt are disperseed
Liquid is uniformly mixed, and the ultrasound 4h at 100W, subsequent magnetic agitation 2h obtain graphene nanobelt/PMMA dispersion liquids.Then by stone
Black alkene nanobelt/PMMA dispersion liquids pour into 500mL absolute ethyl alcohols, and precipitation is filtered and washed 2-3 times with ethyl alcohol, is obtained cotton-shaped
Object.Floccule freeze-drying is removed into remaining DMF and ethyl alcohol for 24 hours.Floccule freeze-drying is removed into solvent for 24 hours, has been dried
Entirely.It is finally that obtained sample is hot-forming at 170 DEG C, 1MPa, finally obtain the nano combined materials of graphene nanobelt/PMMA
Material.
The graphene nanobelt of above-mentioned preparation/PMMA nanocomposites are placed in 3mm molds and are placed in reaction under high pressure
It in kettle, being saturated by supercritical carbon dioxide, saturation pressure 12MPa, saturation temperature is 80 DEG C, saturation time 8h,
Saturation conditions is opened fast decompression valve after completing and is let out to normal pressure, cools down reaction kettle with mixture of ice and water after 30s, obtains
Graphene nanobelt/PMMA fretting map nanocomposites.
The graphene nanobelt that the embodiment obtains/PMMA fretting map nanocomposites, 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：
It weighs 4g PMMA (relative molecular mass 100000) to be added in 40mL DMF solutions, the heating stirring at 100 DEG C
30min makes it fully dissolve, and is cooled to room temperature, and 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.Obtained PMMA colloidal sols and graphene nanobelt are disperseed
Liquid is uniformly mixed, and the ultrasound 4h at 100W, subsequent magnetic agitation 2h obtain graphene nanobelt/PMMA dispersion liquids.Then by stone
Black alkene nanobelt/PMMA dispersion liquids pour into 500mL absolute ethyl alcohols, and precipitation is filtered and washed 2-3 times with ethyl alcohol, is obtained cotton-shaped
Object.Floccule freeze-drying is removed into remaining DMF and ethyl alcohol for 24 hours.Floccule freeze-drying is removed into solvent for 24 hours, has been dried
Entirely.It is finally that obtained sample is hot-forming at 170 DEG C, 1MPa, finally obtain the nano combined materials of graphene nanobelt/PMMA
Material.
The graphene nanobelt of above-mentioned preparation/PMMA nanocomposites are placed in 3mm molds and are placed in reaction under high pressure
It in kettle, is saturated by supercritical carbon dioxide, saturation pressure 16MPa, saturation temperature is 110 DEG C, and saturation time is
12h, saturation conditions are opened fast decompression valve after completing and are let out to normal pressure, cooled down reaction kettle with mixture of ice and water after 30s,
Obtain graphene nanobelt/PMMA fretting map nanocomposites.
The 1.0wt% graphene nanobelts that the embodiment obtains/PMMA fretting map nanocomposites, 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 2.1
×109cells/cm3。
Embodiment 7：
It weighs 4g PMMA (relative molecular mass 100000) to be added in 40mLDMF solution, the heating stirring at 100 DEG C
30min makes it fully dissolve, and is cooled to room temperature, and 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.Obtained PMMA colloidal sols and graphene nanobelt are disperseed
Liquid is uniformly mixed, and the ultrasound 4h at 100W, subsequent magnetic agitation 2h obtain graphene nanobelt/PMMA dispersion liquids.Then by stone
Black alkene nanobelt/PMMA dispersion liquids pour into 500mL absolute ethyl alcohols, and precipitation is filtered and washed 2-3 times with ethyl alcohol, is obtained cotton-shaped
Object.Floccule freeze-drying is removed into remaining DMF and ethyl alcohol for 24 hours.Floccule freeze-drying is removed into solvent for 24 hours, has been dried
Entirely.It is finally that obtained sample is hot-forming at 170 DEG C, 1MPa, finally obtain the nano combined materials of graphene nanobelt/PMMA
Material.
The graphene nanobelt of above-mentioned preparation/PMMA nanocomposites are placed in 3mm molds and are placed in reaction under high pressure
It in kettle, being saturated by supercritical carbon dioxide, saturation pressure 14MPa, saturation temperature is 85 DEG C, saturation time 10h,
Saturation conditions is opened fast decompression valve after completing and is let out to normal pressure, cools down reaction kettle with mixture of ice and water after 30s, obtains
Graphene nanobelt/PMMA fretting map nanocomposites.
The 2.5wt% graphene nanobelts that the embodiment obtains/PMMA fretting map nanocomposites, 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 2.5
×109cells/cm3。
Graphene nanobelt/PMMA fretting maps nanocomposite has higher mechanical property than pure PMMA micro-foaming materials
Energy (under the conditions of same process, as shown in Figure 9) and higher thermal stability (as shown in Figure 10).
Claims (10)
1. the preparation method of graphene nanobelt/PMMA fretting map nanocomposites, it is characterized in that passing through the exhibition of oxidizing process longitudinal direction
It opens multi-wall carbon nano-tube and is in control stannic oxide/graphene nano band, then stannic oxide/graphene nano band is dispersed in DMF high temperatures and is flowed back into
Row reduction obtains graphene nanobelt dispersion liquid, after which is blended with PMMA, through ultrasonic disperse, anti-solvent precipitation, freezing
Dry and hot-forming processing obtains graphene nanobelt/PMMA nanocomposites, then places the nanocomposite
It is placed in progress supercritical carbon dioxide saturation in autoclave in a mold, saturation is finished obtains graphene through quick pressure releasing
Nanobelt/PMMA fretting map nanocomposites.
2. preparation method according to claim 1, it is characterised in that the oxidizing process, specifically：By multi-wall carbon nano-tube
Guan Nong H2SO4After middle stirring, dense H is added3PO4, potassium permanganate is then added and is reacted at 60-70 DEG C, potassium permanganate and multi wall
The mass ratio of carbon nanotube is 1:6, it is subsequently poured into deionized water and dilutes, then pass through H2O2The remaining height with deionized water removal
Potassium manganate is simultaneously washed to neutrality, finally freeze-dried to obtain stannic oxide/graphene nano band.
3. preparation method according to claim 1, it is characterised in that the high temperature reflux, technological parameter are：Reflux
Temperature is 150 DEG C, return time 4h.
4. preparation method according to claim 1, it is characterised in that PMMA average molecular weight is 100000-300000.
5. preparation method according to claim 1, it is characterised in that graphene nanobelt is the 0.1- of the quality of PMMA
5%.
6. preparation method according to claim 1, it is characterised in that the graphene nanobelt, point in DMF
Dissipate a concentration of 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 the hot press forming technology is：Temperature 170-210
DEG C, pressure 1-2MPa.
9. preparation method according to claim 1, it is characterised in that the nano combined materials of graphene nanobelt/PMMA
Expect that the saturation temperature in supercritical carbon dioxide is 60-110 DEG C, saturation pressure 12-18MPa, saturation time 8-12h.
10. graphene nanobelt/PMMA fretting map nanocomposites that in claim 1 to 9 prepared by any the method,
It is characterized in the nanocomposite applications in aerospace, Electronic Packaging or automobile protective field.
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