CN104988592A - 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, be specifically related to polyvinyl alcohol/Graphene composite nano-fiber material and preparation method thereof.
Background technology
Graphene be a kind of by carbon atom with sp
2hybridized orbit composition hexangle type is the flat film of honeycomb lattice, only has the two-dimensional material of a carbon atom thickness, it is a kind of new material of the individual layer laminated structure be made up of carbon atom, it has excellent conduction, heat conduction and mechanical property, thus becomes the desirable Nano filling preparing functional polymer composite.
The preparation of current polymer/graphene composite material mainly adopts blending method, that is: Graphene is directly mixed with polymer or polymer solution, be prepared from through precipitation or the method such as hot-forming, but because graphenic surface is inert condition, extremely weak with the interaction of other medium, and between graphene film and sheet, there is stronger Van der Waals force, very easily reunite, be difficult in polymer or its solution dispersed, the premium properties of Graphene can not be embodied in the composite well, show as the lower and performance heterogeneity of material of Graphene content in composite.
In addition, oxidation-reduction method is one of main method preparing Graphene at present, the method changes graphite into graphite oxide, again graphite oxide reduced, peel off as Graphene, traditional means generally adopts electronation that graphite oxide is reduced to Graphene, but the use of strong reductant (as: hydrazine hydrate) is comparatively large to environmental hazard, and is difficult to removing in last handling process, impacts composite.
Based on the above-mentioned condition of prior art, the preparation method of the present inventor to polymer/graphene composite material studies, object is to provide the preparation method avoiding using the dispersion of reductant, graphene uniform and polymer/graphene composite material easy and simple to handle, is specially polyvinyl alcohol/Graphene composite nano-fiber material and preparation method thereof.
Summary of the invention
In order to overcome the problems referred to above, the present inventor has carried out studying with keen determination to the preparation method of polymer/graphene composite material, found that: the Homogeneous phase mixing liquid first can preparing polyvinyl alcohol/graphene oxide, then be Graphene by graphene oxide in-situ reducing wherein under high-energy ionization radiation, recycling electrostatic spinning technique prepares polyvinyl alcohol/Graphene composite nano-fiber material, avoid introducing strong reductant, Graphene is dispersed in the composite and content is higher, obtained composite nano-fiber material performance is more homogeneous, and the method is easy and simple to handle, environmental protection.
The object of the present invention is to provide following aspect:
(1) preparation method of polyvinyl alcohol/Graphene composite nano-fiber material, the homogeneous mixture solotion of graphene oxide and polyvinyl alcohol is under high-energy ionization radiation, graphene oxide in-situ reducing is Graphene, then utilizes electrostatic spinning technique to prepare polyvinyl alcohol/Graphene composite nano-fiber material.
(2) polyvinyl alcohol/Graphene composite nano-fiber material, this material is prepared from according to preparation method as described in above-mentioned (1).
Below in detail the present invention is described in detail.
According to a first aspect of the invention, the preparation method of polyvinyl alcohol/Graphene composite nano-fiber material is provided, the homogeneous mixture solotion of graphene oxide and polyvinyl alcohol is under high-energy ionization radiation, graphene oxide in-situ reducing is Graphene, then utilizes electrostatic spinning technique to prepare polyvinyl alcohol/Graphene composite nano-fiber material.
The method comprises the following steps:
Step 1), take crystalline flake graphite as raw material, under the effect of the concentrated sulfuric acid, SPA, potassium permanganate and hydrogen peroxide, obtain graphite oxide.
In a preferred embodiment in accordance with the present invention, adopt the Hummers legal system of improvement for graphite oxide, be specially: crystalline flake graphite is added in the mixed liquor of the concentrated sulfuric acid and SPA under cryosel bath condition, potassium permanganate is added under stirring, maintain reaction temperature to stir 1.5 ~ 4 hours below 5 DEG C, reaction system is heated to 30 ~ 35 DEG C and stirring reaction 20 ~ 30 hours, then deionized water and hydrogen peroxide is added, continue stirring reaction 24 ~ 30 hours, filter and use deionized water washing sediment, obtaining described graphite oxide.
Wherein, preferred mass concentration is the concentrated sulfuric acid, the SPA of 85%, the hydrogen peroxide of 25 ~ 35% of 98%; Crystalline flake graphite described in 1g mixes with 4 ~ 6mL concentrated sulfuric acid, and the weight ratio of described crystalline flake graphite and potassium permanganate is 1:7 ~ 1:8; The volume ratio of described SPA and the concentrated sulfuric acid is 1:8 ~ 1:10, and the volume ratio of the described concentrated sulfuric acid and deionized water is 1:4 ~ 1:6, and the volume ratio of described hydrogen peroxide and the concentrated sulfuric acid is 1:1 ~ 1:3; Described mixing speed is 270 ~ 300rpm.
The Hummers method of described improvement comprises low-temp reaction (less than 5 DEG C) and middle temperature reaction (30 ~ 35 DEG C) two stages, in the low-temp reaction stage, main generation sulfuric acid molecule intercalation between graphite flake layer, in the middle temperature stage of reaction, the main deep oxidation of generation graphite and the hydrolysis of intercalation compound, the Hummers method low-temp reaction intercalation of improvement provided by the invention is abundant, middle temperature reaction depth oxidation is complete and hydrolysis is thorough, obtained graphite oxide interlamellar spacing is larger, be easy to the graphene oxide being stripped into individual layer or bilayer, for ultrasonic in subsequent step, the graphene oxide that dispersed with stirring prepares individual layer or bilayer lays the first stone, and pyroreaction (being generally 85 ~ 95 DEG C) stage eliminated in conventional method, reduce energy consumption, improve security, be more suitable for large-scale industrial production.
In a preferred embodiment in accordance with the present invention, the Hummers method of improvement provided by the invention adopts the sodium nitrate in SPA replacement conventional method, the acidity of system can be strengthened, improve oxidation efficiency, the Hummers method of improvement does not produce toxic gas, the easy control of temperature of reaction system, may be used for large-scale production graphene oxide.
Step 2), polyvinyl alcohol is dissolved in deionized water, adds step 1) obtained graphite oxide, ultrasonic and dispersed with stirring, obtains the homogeneous mixture solotion of polyvinyl alcohol/graphene oxide.
In a preferred embodiment in accordance with the present invention, the degree of polymerization of described polyvinyl alcohol is 1700 ~ 1800, in water soluble, ethanol polar solvent.
The mass concentration of described polyvinyl alcohol in its deionized water solution is 8 ~ 10%, the weight ratio of described graphite oxide and polyvinyl alcohol is 1:20 ~ 1:250, and the mass concentration of described graphene oxide in the homogeneous mixture solotion of polyvinyl alcohol/graphene oxide is 4.0 ~ 50.0 ‰.
Ultrasonic, under stirring, described graphite oxide is stripped the graphene oxide into individual layer or bilayer, graphene oxide with carbonyl, carboxyl, the groups such as epoxy radicals make it have stronger hydrophily, dispersed better in water or polar solvent, thus can be dispersed in the aqueous solution of polyvinyl alcohol, in preparation process, the addition of graphene oxide can be improved, thus polyvinyl alcohol/Graphene composite nano-fiber material that obtained Graphene content is higher, improve the multiple performance of composite better, and to mix with polyvinyl alcohol due to Graphene evenly, homogeneity and the stability of composite property are all improved.
Step 3), to step 2) add oxidative free radical scavenger, stirring reaction under high-energy ionization radiation in obtained mixed solution, obtain the homogeneous mixture solotion of polyvinyl alcohol/Graphene.
In a preferred embodiment in accordance with the present invention, described high-energy ionization radiation source is alpha ray, β ray, gamma-rays, X-ray or high-speed electron flow etc., be preferably gamma-rays, the dosage of described high-energy ionization radiation is 20 ~ 80Gy/min, and radiated time is 4 ~ 8 hours.
Under above-mentioned high-energy ionization radiation, there is effects such as ionizing and excite in the water in described mixed solution, generates the H free radical, the aqueous electron e that have compared with strong reducing property
- aqdeng species, generate OH free radical, the H with oxidisability simultaneously
3o
+, H
2, H
2o
2, HO
2deng other species, the e in above-mentioned species
- aqthere is strong reducing property, graphene oxide in-situ reducing in mixed solution can be Graphene and keep dispersed, but owing to there is the OH free radical etc. with strong oxidizing property in system simultaneously, the oxidative free radical in oxidative free radical scavenger removing system need be added, make system entirety keep stronger reducibility.
Described oxidative free radical scavenger is alcohols, and be preferably isopropyl alcohol, the volume ratio of described polyvinyl alcohol/graphene oxide mixed solution and oxidative free radical scavenger is 1:(0.05 ~ 0.4).
Step 4), adopt electrostatic spinning apparatus, with step 3) obtained mixed solution is that spinning solution obtains described polyvinyl alcohol/Graphene composite nano-fiber material.
In a preferred embodiment in accordance with the present invention, in described spinning solution, the mass concentration of polyvinyl alcohol/Graphene is 3.5 ~ 7.0%.
In described electrostatic spinning apparatus, spinning voltage is 10 ~ 28kV, and the distance between emission electrode and collecting electrode is 10 ~ 30cm.
At room temperature, adopt electrostatic spinning apparatus to prepare polyvinyl alcohol/Graphene composite nano fiber or nano fibrous membrane, directly or after processing can be applied to multiple fields.
According to a second aspect of the invention, provide polyvinyl alcohol/Graphene composite nano-fiber material, this material is prepared from according to the preparation method of polyvinyl alcohol as above/Graphene composite nano-fiber material.
In a preferred embodiment in accordance with the present invention, the diameter of described material is 120 ~ 400nm, and fibre length is at more than 8cm.
Graphene uniform, be distributed in described composite nano-fiber material dispersedly, homogeneity and the stability of composite property are all improved, and Graphene mass fraction is in the material 4 ~ 50 ‰, and the area density of described material is 70 ~ 175g/m
2, 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, and electrical conductivity is 190 ~ 255 μ S/cm.
The beneficial effect that the present invention has comprises:
(1) preparation method of polyvinyl alcohol provided by the invention/Graphene composite nano-fiber material at room temperature adopts high-energy ionization radiation that graphene oxide is reduced to Graphene, do not introduce strong reductant, avoid reductant to remain and the destruction of high temperature reduction to organic polymer, and easy and simple to handle, environmental protection;
(2) preparation method of polyvinyl alcohol provided by the invention/Graphene composite nano-fiber material utilizes the feature of graphene oxide good dispersion in water, first prepare the Homogeneous phase mixing liquid of polyvinyl alcohol/graphene oxide, then be Graphene by graphene oxide in-situ reducing wherein, Graphene keeps dispersed in mixed solution, can not assemble agglomerating, obtained composite nano-fiber material performance is more homogeneous;
(3) preparation method of polyvinyl alcohol provided by the invention/Graphene composite nano-fiber material utilizes electrostatic spinning technique to obtain polyvinyl alcohol/Graphene composite nano fiber or nano fibrous membrane, maintain the performance that composite nano materials is homogeneous, and easy and simple to handle;
(4) in polyvinyl alcohol provided by the invention/Graphene composite nano-fiber material, graphene uniform is scattered in polyvinyl alcohol, and material property is more homogeneous, stable, and wherein the content of Graphene is higher, has stronger mechanical performance and electric conductivity.
Accompanying drawing explanation
Fig. 1 illustrates the XRD collection of illustrative plates of polyvinyl alcohol/Graphene composite nano-fiber material;
Fig. 2 illustrates structure chart and the fiber cross section figure of polyvinyl alcohol/Graphene composite nano-fiber material.
Detailed description of the invention
Below by accompanying drawing, experimental example and embodiment, the present invention is described in more detail.Illustrated by these, the features and advantages of the invention will become more explicit.
Embodiment
Embodiment 1
Step 1), 1.2g crystalline graphite powder is added in the concentrated sulfuric acid of 60mL 98%, then the SPA of 6.7mL 85% is added, less than 5 DEG C are cooled in cryosel bath, start slowly stir and add potassium permanganate, maintain reaction temperature less than 5 DEG C to stir 2 hours, remove cryosel bath, reaction system is heated to 35 DEG C and stirring reaction 24 hours, then add 300mL deionized water, after stirring, add the hydrogen peroxide of 30mL 30%, continue stirring reaction 24 ~ 30 hours, filter and use deionized water washing sediment, obtaining described graphite oxide;
Step 2), 0.8g polyvinyl alcohol is added in 9.2g deionized water, heat 2 hours at 60 DEG C, then be warming up to 90 DEG C to keep 1 hour, polyvinyl alcohol is dissolved completely, add 0.016g step 1) obtained graphite oxide, ultrasonic and dispersed with stirring, obtains the homogeneous mixture solotion of polyvinyl alcohol/graphene oxide;
Step 3), to step 2) add 2mL isopropyl alcohol in obtained mixed solution,
60with 80Gy/min dose 6 hours under Co gamma-rays, stirring reaction, obtains the homogeneous mixture solotion of polyvinyl alcohol/Graphene simultaneously;
Step 4), adopt electrostatic spinning apparatus, with step 3) obtained mixed solution is spinning solution, in spinning solution, the mass concentration of polyvinyl alcohol/Graphene is 6.0%, at room temperature, spinning voltage is 18kV, and the distance between emission electrode and collecting electrode is carry out spinning under the condition of 15cm, the described polyvinyl alcohol/Graphene composite nano-fiber material of obtained network structure.
Embodiment 2
Adopt the method similar with embodiment 1 to prepare the polyvinyl alcohol/Graphene composite nano-fiber material of size, network structure that thickness is identical, difference is only: step 2) in add 0.027g graphite oxide.
Embodiment 3
Adopt the method similar with embodiment 1 to prepare the polyvinyl alcohol/Graphene composite nano-fiber material of size, network structure that thickness is identical, difference is only: step 3) in use
209po alpha ray carries out radiation.
Embodiment 4
Adopt the method similar with embodiment 1 to prepare the polyvinyl alcohol/Graphene composite nano-fiber material of size, network structure that thickness is identical, difference is only: step 3) in use
14c β ray carries out radiation.
Embodiment 5
Adopt the method similar with embodiment 1 to prepare the polyvinyl alcohol/Graphene composite nano-fiber material of size, network structure that thickness is identical, difference is only: step 3) in use Cu target X-ray to carry out radiation.
Comparative example
Comparative example 1 solution mixing method prepares polyvinyl alcohol/graphene composite material
Step 1), adopt and embodiment 1 step 1) identical method prepares graphite oxide;
Step 2), by 0.15g step 1) obtained graphite oxide adds in 150mL water, ultrasonic 1 hour, add 0.3g KOH and 2mL hydrazine hydrate, in 98 DEG C of back flow reaction 24 hours, be cooled to room temperature, centrifugation solid product, and with water, ethanol washing, obtain Graphene;
Step 3), 0.8g polyvinyl alcohol is added in 9.2g deionized water, heat 2 hours at 60 DEG C, then be warming up to 90 DEG C to keep 1 hour, polyvinyl alcohol is dissolved completely, add 0.016g step 2) obtained Graphene, ultrasonic and dispersed with stirring, obtains the mixed solution of polyvinyl alcohol/Graphene;
Step 4), by step 3) obtained mixed solution pours in mould, leave standstill after 12 hours in-25 DEG C and take out, dry, obtain and the composite nano-fiber material size of network structure in embodiment 1, sheet polyvinyl alcohol/graphene composite material that thickness is identical.
Comparative example 2 prepares polyvinyl alcohol nano material
Adopt the method similar with embodiment 1 to prepare the polyvinyl alcohol nano material of size, network structure that thickness is identical, difference is only: do not add graphene oxide.
Experimental example
Experimental example 1X-ray diffraction experiments
Use X-ray powder diffraction instrument (Cu target K alpha ray), be 0.15406nm at λ, walk wide by 0.02, operating voltage 40kV, test under the condition of operating current 100mA, embodiment 1 the results are shown in Figure 1, and embodiment 2 ~ 5 result is similar to embodiment 1.
Experimental example 2 Electronic Speculum is tested
Adopt step 4) method, polyvinyl alcohol/Graphene composite nano fiber is prepared on the collecting electrode containing two-sided carbonaceous conductive adhesive tape, take off with above-mentioned composite nano fiber conductive tape, utilize field emission scanning electron microscope (S-4800 type) to observe nanofiber diameter, length etc., test result is shown in Fig. 2.
Experimental example 3
At 25 DEG C, relative air humidity is under the condition of 25 ~ 40%, measures mechanical performance and the electric conductivity of described polyvinyl alcohol/graphene composite material, the results are shown in Table 1.
The performance measurement result of table 1. polyvinyl alcohol/graphene composite material
More than in conjunction with preferred embodiment and exemplary example to invention has been detailed description.But it is to be understood that, these detailed description of the invention are only to illustrative explanations of the present invention, do not form any restriction to protection scope of the present invention.When not exceeding the present invention's spirit and protection domain, can carry out various improvement, equivalencing or modification to the technology of the present invention content and embodiment thereof, these all fall within the scope of protection of the present invention.Protection scope of the present invention is as the criterion with claims.
Claims (10)
1. the preparation method of polyvinyl alcohol/Graphene composite nano-fiber material, it is characterized in that, the homogeneous mixture solotion of graphene oxide and polyvinyl alcohol is under high-energy ionization radiation, graphene oxide in-situ reducing is Graphene, then utilizes electrostatic spinning technique to prepare polyvinyl alcohol/Graphene composite nano-fiber material.
2. preparation method according to claim 1, is characterized in that, the method comprises:
Step 1), take crystalline flake graphite as raw material, under the effect of the concentrated sulfuric acid, SPA, potassium permanganate and hydrogen peroxide, obtain graphite oxide;
Step 2), polyvinyl alcohol is dissolved in deionized water, adds step 1) obtained graphite oxide, ultrasonic and dispersed with stirring, obtains the homogeneous mixture solotion of polyvinyl alcohol/graphene oxide;
Step 3), to step 2) add oxidative free radical scavenger, stirring reaction under high-energy ionization radiation in obtained mixed solution, obtain the homogeneous mixture solotion of polyvinyl alcohol/Graphene;
Step 4), adopt electrostatic spinning apparatus, with step 3) obtained mixed solution is that spinning solution obtains described polyvinyl alcohol/Graphene composite nano-fiber material.
3. preparation method according to claim 1 and 2, it is characterized in that, step 1) in, crystalline flake graphite is added in the mixed liquor of the concentrated sulfuric acid and SPA under cryosel bath condition, under stirring, add potassium permanganate, maintain reaction temperature to stir 1.5 ~ 4 hours below 5 DEG C, reaction system is heated to 30 ~ 35 DEG C and stirring reaction 20 ~ 30 hours, then adds deionized water and hydrogen peroxide, continue stirring reaction 24 ~ 30 hours, filter and washing precipitate, obtain described graphite oxide.
4., according to the preparation method one of claims 1 to 3 Suo Shu, it is characterized in that, step 1) in,
Preferred mass concentration is the concentrated sulfuric acid, the SPA of 85%, the hydrogen peroxide of 25 ~ 35% of 98%, and/or
Crystalline flake graphite described in 1g mixes with 4 ~ 6mL concentrated sulfuric acid, and the weight ratio of described crystalline flake graphite and potassium permanganate is 1:7 ~ 1:8, and/or
The volume ratio of described SPA and the concentrated sulfuric acid is 1:8 ~ 1:10, and the volume ratio of the described concentrated sulfuric acid and deionized water is 1:4 ~ 1:6, and the volume ratio of described hydrogen peroxide and the concentrated sulfuric acid is 1:1 ~ 1:3, and/or
Described mixing speed is 270 ~ 300rpm.
5., according to the preparation method one of Claims 1-4 Suo Shu, it is characterized in that, step 2) in,
The degree of polymerization of described polyvinyl alcohol is 1700 ~ 1800, and/or
The mass concentration of described polyvinyl alcohol in its deionized water solution is 8 ~ 10%, the weight ratio of described graphite oxide and polyvinyl alcohol is 1:20 ~ 1:250, and the mass concentration of described graphene oxide in the homogeneous mixture solotion of polyvinyl alcohol/graphene oxide is 4.0 ~ 50.0 ‰.
6., according to the preparation method one of claim 1 to 5 Suo Shu, it is characterized in that, step 3) in,
Described oxidative free radical scavenger is alcohols, is preferably isopropyl alcohol, and/or
The volume ratio of described polyvinyl alcohol/graphene oxide mixed solution and oxidative free radical scavenger is 1:(0.05 ~ 0.4), and/or
Described high-energy ionization radiation source is alpha ray, β ray, gamma-rays, X-ray or high-speed electron flow etc., is preferably gamma-rays, and/or
The dosage of described high-energy ionization radiation is 20 ~ 80Gy/min, and radiated time is 4 ~ 8 hours.
7., according to the preparation method one of claim 1 to 6 Suo Shu, it is characterized in that, step 4) in,
In described spinning solution, the mass concentration of polyvinyl alcohol/Graphene is 3.5 ~ 7.0%, and/or
In described electrostatic spinning apparatus, spinning voltage is 10 ~ 28kV, and the distance between emission electrode and collecting electrode is 10 ~ 30cm.
8. polyvinyl alcohol/Graphene composite nano-fiber material, is characterized in that, this material is prepared from according to the described preparation method of one of claim 1 to 7.
9. composite nano-fiber material according to claim 8, is characterized in that, the diameter of described material is 120 ~ 400nm, and fibre length is at more than 8cm.
10. nano-fiber material according to claim 8 or claim 9, it is characterized in that, graphene uniform, be distributed in described composite nano-fiber material dispersedly, Graphene mass fraction is in the material 4 ~ 50 ‰, and the area density of described material is 70 ~ 175g/m
2, 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, and electrical conductivity is 190 ~ 255 μ S/cm.
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| CN110484980A (en) * | 2019-07-31 | 2019-11-22 | 郑州市君友纺织品织造有限公司 | A kind of composite thermal fabric and preparation method thereof |
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