CN104988592B - Polyvinyl alcohol/graphene composite nano fiber material and preparation method thereof - Google Patents
Polyvinyl alcohol/graphene composite nano fiber material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a polyvinyl alcohol/graphene composite nano fiber material and a preparation method thereof. A modified Hummers method is adopted to prepare oxidized graphite, then a uniform polyvinyl alcohol/graphene oxide mixed solution is prepared, the mixed solution is subjected to high-energy ionizing radiation to in-situ reduce the oxidized graphene into graphene, and finally a static spinning technology is adopted to prepare the polyvinyl alcohol/graphene composite nano fiber material. The provided preparation method has the advantages that (1) a strong reducing agent is not introduced into the system; (2) graphene is evenly dispersed in the composite material, and the graphene content is higher; (3) the performance of the prepared composite nano fiber material is more uniform and the mechanical properties and electro-conductive performance are stronger; (4) the operation of the preparation method is convenient, and the preparation method is environment-friendly.
Description
Technical field
The invention belongs to organic polymer/composite material of inorganic matter field, and in particular to polyvinyl alcohol/Graphene is compound to be received
Rice fibrous material and preparation method thereof.
Background technology
Graphene be one kind by carbon atom with sp2Hybrid orbital flat film of the composition hexangle type in honeycomb lattice, only
The two-dimensional material of one carbon atom thickness, is a kind of new material of the monolayer laminated structure being made up of carbon atom, and it has excellent
Conduction, heat conduction and mechanical property, thus become the preferable Nano filling for preparing functional polymer composite.
The preparation of polymer/graphene composite material at present mainly adopts blending method, i.e.,：By Graphene and polymer or poly-
Polymer solution directly mixes, and Jing precipitations or the method such as hot-forming are prepared from, but due to the inert state of graphenic surface, with
The interaction of other media is extremely weak, and there is stronger Van der Waals force between graphene film and piece, easily reunites, it is difficult to
It is dispersed in polymer or its solution, it is impossible to which that the premium properties of Graphene is embodied well in the composite, performance
For Graphene content in composite is relatively low and performance heterogeneity of material.
Additionally, oxidation-reduction method is to prepare one of main method of Graphene at present, graphite is changed into oxidation by the method
Graphite, then be Graphene by graphite oxide reduction, stripping, graphite oxide is typically reduced to stone by traditional means using electronation
Black alkene, but strong reductant is (such as：Hydrazine hydrate) use it is larger to environmental hazard, and be difficult to remove in last handling process, to compound
Material is impacted.
Based on the above-mentioned condition of prior art, the present inventor is carried out to the preparation method of polymer/graphene composite material
Research, it is therefore an objective to which offer avoids using reducing agent, graphene uniform dispersion and polymer/graphene composite material easy to operate
Preparation method, specially polyvinyl alcohol/Graphene composite nano-fiber material and preparation method thereof.
The content of the invention
In order to overcome the problems referred to above, the present inventor to carry out with keen determination the preparation method of polymer/graphene composite material
Research, as a result finds：The uniform mixed liquor of polyvinyl alcohol/graphene oxide can be first prepared, then under high-energy ionization radiation
It is Graphene by graphene oxide in-situ reducing therein, recycles electrostatic spinning technique to prepare polyvinyl alcohol/Graphene and be combined
Nano-fiber material, it is to avoid introduce strong reductant, Graphene is dispersed in the composite and content is higher, it is obtained compound
Nano-fiber material performance is more homogeneous, and the method is easy to operate, environmental protection.
It is an object of the invention to provide following aspect：
(1) preparation method of polyvinyl alcohol/Graphene composite nano-fiber material, graphene oxide is equal with polyvinyl alcohol
Under high-energy ionization radiation, graphene oxide in-situ reducing is Graphene to even mixed solution, then using electrostatic spinning technique system
Standby polyvinyl alcohol/Graphene composite nano-fiber material.
(2) polyvinyl alcohol/Graphene composite nano-fiber material, the material is according to (1) the preparation method system as described above
It is standby to form.
The present invention described below.
According to the first aspect of the invention, there is provided the preparation method of polyvinyl alcohol/Graphene composite nano-fiber material, oxygen
Under high-energy ionization radiation, graphene oxide in-situ reducing is Graphene to the homogeneous mixture solotion of graphite alkene and polyvinyl alcohol,
Then polyvinyl alcohol/Graphene composite nano-fiber material is prepared using electrostatic spinning technique.
The method is comprised the following steps：
Step 1), with crystalline flake graphite as raw material, in the presence of concentrated sulphuric acid, strong phosphoric acid, potassium permanganate and hydrogen peroxide, obtain
Graphite oxide.
In a preferred embodiment in accordance with the present invention, graphite oxide is prepared using the Hummers methods of improvement, specially：
Crystalline flake graphite is added in mixed liquor of the concentrated sulphuric acid with strong phosphoric acid under the conditions of ice salt bath, stirring is lower to add potassium permanganate, maintains
Reaction temperature is stirred below 1.5~4 hours at 5 DEG C, and reaction system is heated to into 30~35 DEG C of simultaneously stirring reaction 20~30 hours,
Deionized water and hydrogen peroxide are subsequently adding, continue stirring reaction 24~30 hours, filter and be washed with deionized precipitate, obtained
To the graphite oxide.
Wherein, preferred mass concentration is 98% concentrated sulphuric acid, 85% strong phosphoric acid, 25~35% hydrogen peroxide；Described in 1g
Crystalline flake graphite mixes with 4~6mL concentrated sulphuric acids, and the crystalline flake graphite is 1 with the weight ratio of potassium permanganate:7~1:8；The dense phosphorus
Acid is 1 with the volume ratio of concentrated sulphuric acid:8~1:10, the concentrated sulphuric acid is 1 with the volume ratio of deionized water:4~1:6, the dioxygen
Water is 1 with the volume ratio of concentrated sulphuric acid:1~1:3；The mixing speed is 270~300rpm.
The Hummers methods of the improvement include low-temp reaction (less than 5 DEG C) and middle temperature reaction (30~35 DEG C) two stages,
It is main that sulfuric acid molecule intercalation between graphite flake layer occurs in the low-temp reaction stage, in the middle temperature stage of reaction, main generation graphite
The hydrolysis of deep oxidation and intercalation compound, the Hummers method low-temp reactions intercalation of the improvement that the present invention is provided is abundant, in
Warm reaction depth oxidation is completely and hydrolysis is thorough, and obtained graphite oxide interlamellar spacing is bigger, it is easy to be stripped into monolayer or bilayer
Graphene oxide, be in subsequent step ultrasound, dispersed with stirring prepares monolayer or the graphene oxide of bilayer lays the first stone, and save
In pyroreaction (generally 85~95 DEG C) stage gone in conventional method, energy consumption is reduced, improve safety, be more suitable for big
Technical scale is produced.
In a preferred embodiment in accordance with the present invention, the Hummers methods of the improvement that the present invention is provided are taken using strong phosphoric acid
For the sodium nitrate in conventional method, the acidity of system can be strengthened, improve oxidation efficiency, the Hummers methods of improvement have not been produced
Poisonous gas, the easy control of temperature of reaction system can be used for large-scale production graphene oxide.
Step 2), polyvinyl alcohol is dissolved in deionized water, add step 1) obtained in graphite oxide, ultrasound and stirring divide
Dissipate, obtain the homogeneous mixture solotion of polyvinyl alcohol/graphene oxide.
In a preferred embodiment in accordance with the present invention, the degree of polymerization of the polyvinyl alcohol is 1700~1800, is dissolved in
In water, ethanol polar solvent.
Mass concentration of the polyvinyl alcohol in its deionized water solution is 8~10%, the graphite oxide and poly- second
The weight ratio of enol is 1:20~1:250, the graphene oxide is in the homogeneous mixture solotion of polyvinyl alcohol/graphene oxide
Mass concentration be 4.0~50.0 ‰.
Under ultrasound, stirring, the graphite oxide is stripped the graphene oxide for monolayer or bilayer, graphene oxide band
The groups such as some carbonyls, carboxyl, epoxy radicals make it have stronger hydrophilic, and dispersibility is more preferable in water or polar solvent, because
And can be dispersed in the aqueous solution of polyvinyl alcohol, in preparation process, the addition of graphene oxide can be improved, so as to make
Higher polyvinyl alcohol/Graphene the composite nano-fiber material of Graphene content is obtained, preferably improves the diversity of composite
Can, and, the homogeneity and stability of composite property are improved due to Graphene and polyvinyl alcohol evenly.
Step 3), to step 2) obtained in oxidative free radical scavenger is added in mixed solution, in high-energy ionization radiation
Lower stirring reaction, obtains the homogeneous mixture solotion of polyvinyl alcohol/Graphene.
In a preferred embodiment in accordance with the present invention, the high-energy ionization radiation source is alpha ray, β rays, gamma-rays, X
Ray or high-speed electron flow etc., preferably gamma-rays, the dosage of the high-energy ionization radiation is 20~80Gy/min, radiated time
For 4~8 hours.
Under above-mentioned high-energy ionization radiation, there is the effects such as ionize and excite in the water in the mixed solution, and generation has
H free radicals, aqueous electron e compared with strong reducing property- aqDeng species, while generating OH free radicals, H with oxidisability3O+、
H2、H2O2、HO2Deng other species, the e in above-mentioned species- aqWith strong reducing property, can be former by the graphene oxide in mixed solution
Position is reduced to Graphene and keeps dispersed, but due to there is OH free radicals with strong oxidizing property etc. in system simultaneously,
The oxidative free radical in oxidative free radical scavenger removing system need to be added, makes system integrally keep stronger reproducibility.
The oxidative free radical scavenger is alcohols, preferably isopropanol, and the polyvinyl alcohol/graphene oxide mixes
Solution is 1 with the volume ratio of oxidative free radical scavenger:(0.05~0.4).
Step 4), using electrostatic spinning apparatus, with step 3) obtained in mixed solution the poly- second is obtained as spinning solution
Enol/Graphene composite nano-fiber material.
In a preferred embodiment in accordance with the present invention, in the spinning solution polyvinyl alcohol/Graphene mass concentration
For 3.5~7.0%.
In the electrostatic spinning apparatus, spinning voltage is 10~28kV, and the distance between emission electrode and receiving electrode are
10~30cm.
At room temperature, polyvinyl alcohol/Graphene composite nano fiber or Nanowire are prepared using electrostatic spinning apparatus
Dimension film, can it is direct or processed after be applied to multiple fields.
According to the second aspect of the invention, there is provided polyvinyl alcohol/Graphene composite nano-fiber material, the material is according to such as
The preparation method of upper described polyvinyl alcohol/Graphene composite nano-fiber material is prepared from.
In a preferred embodiment in accordance with the present invention, a diameter of 120~400nm of the material, fibre length is in 8cm
More than.
Graphene uniform, be dispersedly distributed in the composite nano-fiber material, the homogeneity of composite property and
Stability is improved, and Graphene mass fraction in the material is 4~50 ‰, and the area density of the material is 70
~175g/m2, tensile strength be 20.7~23.9MPa, elongation at break be 13~20%, Young's modulus of elasticity be 11.0~
12.0MPa, electrical conductivity is 190~255 μ S/cm.
The present invention have the advantage that including：
(1) preparation method of polyvinyl alcohol/Graphene composite nano-fiber material that the present invention is provided is adopted at room temperature
Graphene oxide is reduced to Graphene by high-energy ionization radiation, do not introduce strong reductant, it is to avoid reducing agent residual and high temperature are also
The former destruction to organic polymer, and easy to operate, environmental protection；
(2) preparation method of polyvinyl alcohol/Graphene composite nano-fiber material that the present invention is provided utilizes graphite oxide
Alkene prepares the uniform mixed liquor of polyvinyl alcohol/graphene oxide in water the characteristics of good dispersion, first, then by oxidation therein
Graphene in-situ reducing is Graphene, and Graphene keeps dispersed in mixed solution, will not assemble agglomerating, obtained compound
Nano-fiber material performance is more homogeneous；
(3) preparation method of polyvinyl alcohol/Graphene composite nano-fiber material that the present invention is provided utilizes electrostatic spinning
Technology is obtained polyvinyl alcohol/Graphene composite nano fiber or nano fibrous membrane, maintains the homogeneous performance of composite nano materials,
And it is easy to operate；
(4) graphene uniform is scattered in poly- second in polyvinyl alcohol/Graphene composite nano-fiber material that the present invention is provided
In enol, material property is more homogeneous, stable, and the content of wherein Graphene is higher, with higher mechanical performance and electric conductivity
Energy.
Description of the drawings
Fig. 1 illustrates the XRD spectrum of polyvinyl alcohol/Graphene composite nano-fiber material；
Fig. 2 illustrates the structure chart and fiber cross section figure of polyvinyl alcohol/Graphene composite nano-fiber material.
Specific embodiment
Below by accompanying drawing, experimental example and embodiment, the present invention is described in more detail.By these explanations, the present invention
The characteristics of and advantage will become more apparent from clearly.
Embodiment
Embodiment 1
Step 1), 1.2g crystalline graphite powders are added in the concentrated sulphuric acid of 60mL 98%, it is subsequently adding the dense of 6.7mL 85%
Phosphoric acid, is cooled to less than 5 DEG C in ice salt bath, starts to be slowly stirred and add potassium permanganate, maintains to be stirred below 5 DEG C of reaction temperature
Mix 2 hours, remove ice salt bath, reaction system is heated to into 35 DEG C of simultaneously stirring reaction 24 hours, be subsequently adding 300mL deionizations
Water, is stirring evenly and then adding into the hydrogen peroxide of 30mL 30%, continues stirring reaction 24~30 hours, filters and is washed with deionized water
Precipitate is washed, the graphite oxide is obtained；
Step 2), 0.8g polyvinyl alcohol is added in 9.2g deionized waters, heat 2 hours at 60 DEG C, then heat to
90 DEG C keep 1 hour, be completely dissolved polyvinyl alcohol, add 0.016g steps 1) obtained in graphite oxide, ultrasound and stirring divide
Dissipate, obtain the homogeneous mixture solotion of polyvinyl alcohol/graphene oxide；
Step 3), to step 2) obtained in 2mL isopropanols are added in mixed solution,60With 80Gy/min under Co gamma-rays
Dose 6 hours, while stirring reaction, obtains the homogeneous mixture solotion of polyvinyl alcohol/Graphene；
Step 4), using electrostatic spinning apparatus, with step 3) obtained in mixed solution as spinning solution, in spinning solution gather
The mass concentration of vinyl alcohol/Graphene is 6.0%, and at room temperature, spinning voltage is 18kV, between emission electrode and receiving electrode
Distance be 15cm under conditions of carry out spinning, be obtained network structure the polyvinyl alcohol/Graphene composite nano fiber material
Material.
Embodiment 2
Polyvinyl alcohol/the graphite of size, thickness identical network structure is prepared using method similar to Example 1
Alkene composite nano-fiber material, differs only in：Step 2) middle addition 0.027g graphite oxides.
Embodiment 3
Polyvinyl alcohol/the graphite of size, thickness identical network structure is prepared using method similar to Example 1
Alkene composite nano-fiber material, differs only in：Step 3) used in209Po alpha rays are radiated.
Embodiment 4
Polyvinyl alcohol/the graphite of size, thickness identical network structure is prepared using method similar to Example 1
Alkene composite nano-fiber material, differs only in：Step 3) used in14C β rays are radiated.
Embodiment 5
Polyvinyl alcohol/the graphite of size, thickness identical network structure is prepared using method similar to Example 1
Alkene composite nano-fiber material, differs only in：Step 3) used in Cu target X-rays radiated.
Comparative example
The solution mixing method of comparative example 1 prepares polyvinyl alcohol/graphene composite material
Step 1), using and the step 1 of embodiment 1) identical method prepares graphite oxide；
Step 2), by 0.15g steps 1) obtained in graphite oxide add 150mL water in, ultrasound 1 hour, add 0.3g
KOH and 2mL hydrazine hydrates, in 98 DEG C of back flow reaction 24 hours, are cooled to room temperature, centrifugation solid product, and are washed with water, ethanol
Wash, obtain Graphene；
Step 3), 0.8g polyvinyl alcohol is added in 9.2g deionized waters, heat 2 hours at 60 DEG C, then heat to
90 DEG C keep 1 hour, be completely dissolved polyvinyl alcohol, add 0.016g steps 2) obtained in Graphene, ultrasound and dispersed with stirring,
Obtain the mixed solution of polyvinyl alcohol/Graphene；
Step 4), by step 3) obtained in mixed solution pour in mould, in -25 DEG C stand 12 hours after take out, drying,
Obtain multiple with the composite nano-fiber material size of network structure, thickness identical lamellar polyvinyl alcohol/Graphene in embodiment 1
Condensation material.
Comparative example 2 prepares polyvinyl alcohol nano material
The polyvinyl alcohol nano of size, thickness identical network structure is prepared using method similar to Example 1
Fibrous material, differs only in：Without graphene oxide.
Experimental example
Experimental example 1X- ray diffraction experiments
It is 0.15406nm in λ using X-ray powder diffraction instrument (Cu target K alpha rays), step width 0.02, running voltage
40kV, is tested under conditions of operating current 100mA, and the result of embodiment 1 is shown in Fig. 1, the result of embodiment 2~5 and the phase of embodiment 1
Seemingly.
The Electronic Speculum of experimental example 2 is tested
Using step 4) method, polyvinyl alcohol/Graphene composite nano fiber is prepared into containing two-sided carbonaceous conductive adhesive tape
Receiving electrode on, remove with above-mentioned composite nano fiber conductive tape, using field emission scanning electron microscope (S-4800 types) see
Nanofiber diameter, length etc. are examined, test result is shown in Fig. 2.
Experimental example 3
At 25 DEG C, relative air humidity is under conditions of 25~40%, to determine the polyvinyl alcohol/graphene composite material
Mechanical performance and electric conductivity, the results are shown in Table 1.
The performance measurement result of 1. polyvinyl alcohol of table/graphene composite material
The present invention has been described in detail above in association with preferred implementation and exemplary example.But need statement
It is that these specific embodiments are only the illustrative explanations to the present invention, do not constitute any limit to protection scope of the present invention
System.In the case of without departing from spirit and scope of the present invention, the technology of the present invention content and embodiments thereof can be carried out
Various improvement, equivalencing or modification, these are each fallen within protection scope of the present invention.Protection scope of the present invention is with appended power
Profit requires to be defined.
Claims (5)
1. the preparation method of polyvinyl alcohol/Graphene composite nano-fiber material, it is characterised in that the method includes：
Step 1), crystalline flake graphite is added in mixed liquor of the concentrated sulphuric acid with strong phosphoric acid under the conditions of ice salt bath, the lower addition of stirring is high
Potassium manganate, maintains reaction temperature stirred below 1.5~4 hours at 5 DEG C, and reaction system is heated to into 30~35 DEG C and stirring reaction
20~30 hours, deionized water and hydrogen peroxide are subsequently adding, continue stirring reaction 24~30 hours, filtered and washing precipitate,
Obtain graphite oxide；
Step 2), polyvinyl alcohol is dissolved in deionized water, add step 1) obtained in graphite oxide, ultrasound and dispersed with stirring,
The homogeneous mixture solotion of polyvinyl alcohol/graphene oxide is obtained, quality of the polyvinyl alcohol in its deionized water solution is dense
Spend for 8~10%, the graphite oxide is 1 with the weight ratio of polyvinyl alcohol:20~1:250, the graphene oxide is in poly- second
Mass concentration in the homogeneous mixture solotion of enol/graphene oxide is 4.0~50.0 ‰；
Step 3), to step 2) obtained in oxidative free radical scavenger is added in mixed solution, stir under high-energy ionization radiation
Reaction is mixed, the homogeneous mixture solotion of polyvinyl alcohol/Graphene is obtained；
Step 4), using electrostatic spinning apparatus, with step 3) obtained in mixed solution as spinning solution, in the spinning solution gather
The mass concentration of vinyl alcohol/Graphene be 3.5~7.0%, and the electrostatic spinning apparatus in, spinning voltage be 10~
The distance between 28kV, emission electrode and receiving electrode are 10~30cm, the polyvinyl alcohol/Graphene composite Nano are obtained fine
Dimension material, a diameter of 120~400nm of the material, fibre length graphene uniform, is dispersedly distributed in institute in more than 8cm
In stating composite nano-fiber material, Graphene mass fraction in the material is 4~50 ‰, the area density of the material
For 70~175g/m2, tensile strength is 20.7~23.9MPa, and elongation at break is 13~20%, and Young's modulus of elasticity is 11.0
~12.0MPa, electrical conductivity is 190~255 μ S/cm.
2. preparation method according to claim 1, it is characterised in that step 1) in,
Concentrated sulphuric acid, 85% strong phosphoric acid, 25~35% hydrogen peroxide that mass concentration is 98% are selected, and/or
Crystalline flake graphite described in 1g mixes with 4~6mL concentrated sulphuric acids, and the crystalline flake graphite is 1 with the weight ratio of potassium permanganate:7~1:
8, and/or
The strong phosphoric acid is 1 with the volume ratio of concentrated sulphuric acid:8~1:10, the concentrated sulphuric acid is 1 with the volume ratio of deionized water:4~
1:6, the hydrogen peroxide is 1 with the volume ratio of concentrated sulphuric acid:1~1:3, and/or
The mixing speed is 270~300rpm.
3. preparation method according to claim 1, it is characterised in that step 2) in, the degree of polymerization of the polyvinyl alcohol is
1700~1800.
4. preparation method according to claim 1, it is characterised in that step 3) in,
The oxidative free radical scavenger is alcohols, and/or
The polyvinyl alcohol/graphene oxide mixed solution is 1 with the volume ratio of oxidative free radical scavenger:(0.05~
0.4), and/or
The high-energy ionization radiation source be alpha ray, β rays, gamma-rays, X-ray or high-speed electron flow, and/or
The dosage of the high-energy ionization radiation is 20~80Gy/min, and radiated time is 4~8 hours.
5. preparation method according to claim 4, it is characterised in that step 3) in,
The oxidative free radical scavenger is isopropanol, and/or
The high-energy ionization radiation source is gamma-rays.
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Families Citing this family (7)
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| CN105220247A (en) * | 2015-11-13 | 2016-01-06 | 北京石油化工学院 | A kind of method regulating Electrospun diameter |
| CN106093166A (en) * | 2016-06-07 | 2016-11-09 | 上海烟草集团有限责任公司 | Based on material with carbon element for electrode detecting nicotine and its preparation method and application |
| CN106702568A (en) * | 2016-11-17 | 2017-05-24 | 无锡市长安曙光手套厂 | Graphene anti-radiation fiber fabric |
| CN107447280A (en) * | 2017-08-17 | 2017-12-08 | 重庆大学 | A kind of preparation method of graphene quantum dot/polyvinyl alcohol hollow Nano fiber in use |
| CN110484980B (en) * | 2019-07-31 | 2021-10-08 | 郑州市君友纺织品织造有限公司 | Composite thermal fabric and preparation method thereof |
| CN110424100B (en) * | 2019-08-06 | 2021-07-20 | 深圳市前海大众鑫环保科技有限公司 | Total heat exchange graphene nanofiber membrane and preparation method thereof |
| CN114875499A (en) * | 2022-05-16 | 2022-08-09 | 绍兴渠广纺织有限公司 | Composite fiber warp-knitted fabric and preparation process thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101559941A (en) * | 2009-05-26 | 2009-10-21 | 上海大学 | Method for preparing graphite alkenyl nanometer materials by electron beam irradiation method |
| CN102408109A (en) * | 2011-08-23 | 2012-04-11 | 中国科学院上海应用物理研究所 | Reduced graphene oxide and preparation method thereof |
| CN102690426A (en) * | 2012-06-08 | 2012-09-26 | 浙江大学 | Method for preparing graphene/polymer composite material based on infrared irradiation |
| CN104437415A (en) * | 2015-01-05 | 2015-03-25 | 福州大学 | Modified-chitosan and graphite oxide magnetic nano absorbent and preparation and application thereof |
| CN104451925A (en) * | 2014-11-21 | 2015-03-25 | 东华大学 | Water-soluble polymer/graphene composite fiber as well as preparation method and application thereof |
-
2015
- 2015-07-17 CN CN201510423397.XA patent/CN104988592B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101559941A (en) * | 2009-05-26 | 2009-10-21 | 上海大学 | Method for preparing graphite alkenyl nanometer materials by electron beam irradiation method |
| CN102408109A (en) * | 2011-08-23 | 2012-04-11 | 中国科学院上海应用物理研究所 | Reduced graphene oxide and preparation method thereof |
| CN102690426A (en) * | 2012-06-08 | 2012-09-26 | 浙江大学 | Method for preparing graphene/polymer composite material based on infrared irradiation |
| CN104451925A (en) * | 2014-11-21 | 2015-03-25 | 东华大学 | Water-soluble polymer/graphene composite fiber as well as preparation method and application thereof |
| CN104437415A (en) * | 2015-01-05 | 2015-03-25 | 福州大学 | Modified-chitosan and graphite oxide magnetic nano absorbent and preparation and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 《Reduction and disorder in graphene oxide induced by electron-beam irradiation》;Lei Chen et al.;《Materials Letters》;20110202;第65卷;第1229-1230页 * |
| 《Reduction of graphene by electron beam generated plasmas produced in methane/argon mixtures》;M.Baraket et al.;《Carbon》;20100525;第48卷(第12期);第3382-3390页 * |
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