CN108219179A - A kind of plant nanometer cellulose base flexible electromagnetic shielding film and its preparation method and application - Google Patents
A kind of plant nanometer cellulose base flexible electromagnetic shielding film and its preparation method and application Download PDFInfo
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Abstract
The invention belongs to technical field of function materials, and in particular to a kind of plant nanometer cellulose base flexible electromagnetic shielding film and its preparation method and application.Above-mentioned preparation method step is：(1) finely dispersed nano silver stannic oxide/graphene nano cellulose dispersion liquid is prepared；The nano silver gross mass is the 1%~10% of graphene oxide gross mass, and graphene oxide gross mass is the 5%~20% of nano-cellulose gross mass；(2) it will be filtered by vacuum and form a film after above-mentioned dispersion liquid ultrasound deaeration, nano silver stannic oxide/graphene nano cellulose composite membrane is obtained after dry；(3) step (2) the nano silver stannic oxide/graphene nano cellulose composite membrane with vitamin C is restored, obtains nano silver graphene nano fiber element composite membrane.The preparation method preparation process of the present invention is simple, easily operated and production；Gained composite membrane has antibacterial and electromagnetic shielding action, has a good application prospect.
Description
Technical field
The invention belongs to technical field of function materials, and in particular to a kind of plant nanometer cellulose base flexible electromagnetic shielding film
And its preparation method and application.
Background technology
Electromagnetic shielding film can effectively block the radiation of the various Eavesdropping conventional frequencies such as radio wave, infrared, ultraviolet, from
And it can successfully block electronic eavesdropping.The new technology of existing electromagnetic shielding film be by tin indium oxide (ITO) vacuum sputtering on base material,
But manufacturing cost is high, not environmentally, and screened film is easy to grow bacterium during daily use, very unhygienic, therefore
There are antibacterial effect, of low cost, environmentally protective electromagnetic shielding film there is an urgent need to develop a kind of.
Nano-cellulose is a kind of green environment protective biological material, good thickening property, rheological characteristic, film forming and dispersion
Property, and its tensile strength is high, and it can high temperature resistant and low temperature.Membrane material is prepared with environmentally protective by raw material of nano-cellulose
Etc. many characteristics, but simple nano-cellulose film does not have effectiveness and service life is shorter.
Important growth of the graphene oxide as graphene, because more oxygen-containing functional group is contained on its surface, promotes to aoxidize
Graphene platelet has very strong water-wet behavior, so as to be easily dispersed in water and organic solvent.In addition, graphene oxide thin slice has
There are larger specific surface area and a large amount of carboxyl functional groups, promote it compound with other materials.Graphene composite wood is prepared at this stage
Material, is largely that graphene is added directly into composite material, but graphene has larger specific surface area, graphene sheet layer
Between there is very strong Van der Waals force, generate conjugatedπbond, in the drying process of composite membrane, it is poly- that wadding can occur for graphene, graphite
The poly- strength character for largely influencing composite film material of wadding of alkene.Therefore, the wadding of graphene in the composite is solved to gather
Problem has realistic meaning.
Nano silver is that grain size is accomplished nano level metallic silver simple substance, there is strong bacteriostasis.
104403132 A of CN disclose a kind of preparation method of cellulose based nano silver composite material, are changed using carboxylated
The nano-cellulose of property is as Ag+Carrier, stabilizer and reducing agent, product made from the invention only has antibiotic property, do not have
Conductive and shielding properties.
105419530 A of CN disclose a kind of graphene nano silver antibiotic paint and preparation method thereof, and the invention is by graphite
Alkene and nano silver are directly scattered in dispersion liquid, are easy to wadding and are gathered, are unable to reach finely dispersed effect.
105772739 A of CN disclose a kind of preparation method of graphene/nano silver composite antibacterial material, will be adsorbed with
The graphene oxide of silver ion, which is put into reducing agent solution, to be heated, and is centrifuged up to graphene/nano silver composite material,
In the invention：(1) reducing agent used is glyoxalic acid is toxic, be corrosive, can stimulate skin and mucous membrane；(2) by Adsorption For Ag from
The graphene oxide of son is directly placed into reducing agent, and silver ion is easily dissolved in solution again.
Invention content
In order to more than solving in the prior art reducing agent not environmentally, in place of the non-uniform shortcoming and defect of graphene dispersion,
The primary and foremost purpose of the present invention is to provide a kind of preparation method of plant nanometer cellulose base flexible electromagnetic shielding film.
The plant nanometer cellulose base flexibility electromagnetic screen obtained another object of the present invention is to provide above-mentioned preparation method
Cover film.
It is still another object of the present invention to provide the applications of above-mentioned plant nanometer cellulose base flexible electromagnetic shielding film.
The present invention technical solution be：
A kind of preparation method of plant nanometer cellulose base flexible electromagnetic shielding film, includes the following steps：
(1) raw material nano silver, graphene oxide and nano-cellulose dispersion liquid are taken, finely dispersed nanometer is prepared with solvent
Silver-graphene oxide-nano-cellulose dispersion liquid；Wherein nano silver gross mass is the 1%~20% of graphene oxide gross mass,
Graphene oxide gross mass is the 5%~10% of nano-cellulose gross mass；The solvent is water, methanol, ethyl alcohol, second two
One or more of alcohol, glycerine, butanol or n-amyl alcohol；
(2) it will be filtered by vacuum and form a film after step (1) the dispersion liquid ultrasound deaeration, nano silver-oxidation stone is obtained after dry
Black alkene-nano cellulose composite film；
(3) step (2) nano silver-graphene oxide-nano cellulose composite film with vitamin C is restored, obtained
Nanometer silver-graphene-nano cellulose composite film, that is, plant nanometer cellulose base flexible electromagnetic shielding film.
Above-mentioned graphene oxide can be made by hummers methods, and commercial product also can be used directly.
Preferably, the solvent of step (1) described dispersion liquid is water.
Preferably, the nano silver grain size is 25~100nm；It is furthermore preferred that the grain size of nano silver is 25~50nm.
Nano silver not only has extraordinary antibacterial effect, also good electric conductivity.It is mixed into and receives in nano-cellulose film
Meter Yin can not only extend the service life of film, moreover it is possible to achieve the effect that electromagnetic shielding.In this size, nano silver is easy to adsorb
On graphene oxide；The present invention is by the graphene oxide in finely dispersed graphene oxide-nano silver-nano-cellulose film
In-situ reducing is graphene, solves the problems, such as that graphene dispersion is non-uniform.
Preferably, above-mentioned graphene oxide individual layer rate is 50%~80%, and piece diameter is 100nm~1 μm, and thickness in monolayer is
0.8nm~1.2nm.
It is furthermore preferred that graphene oxide individual layer rate is 70%~80%, piece diameter is 100nm~200nm, and thickness in monolayer is
0.8nm~1.0nm.
Preferably, step (1) the specific steps are：
(a) graphene oxide is disperseed with solvent, then nano silver is added in graphene oxide dispersion and stirred
Obtain finely dispersed nano silver-graphene oxide dispersion；
(b) the finely dispersed nano silver-graphene oxide dispersion for obtaining step (a) and nano-cellulose dispersion liquid
It is mixed and stirred for obtaining finely dispersed nano silver-graphene oxide-nano-cellulose dispersion liquid.
Above-mentioned a concentration of 1mg/mL~2mg/mL of graphene oxide dispersion；Nano-cellulose dispersion liquid mass concentration is
0.1%~1%.
Preferably, the supersonic frequency of step (2) the ultrasonic deaeration is 300~400w, 15~60min of time.
Preferably, vitamin C quality is 5~10 times of graphene oxide quality in step (3), reduction reaction temperature 40
~60 DEG C, the reaction time is 1~5h.
Electromagnetic shielding film made from the preparation method of above-mentioned plant nanometer cellulose base flexible electromagnetic shielding film.
Relative to the prior art, the present invention has the following advantages：
(1) plant nanometer cellulose base flexible electromagnetic shielding film provided by the invention is simple for process, and preparation process is to ring
Border is pollution-free, it can be achieved that large-scale production；
(2) present invention is in situ by the graphene oxide in finely dispersed graphene oxide-nano silver-nano-cellulose film
Graphene is reduced to, solves the problems, such as that graphene dispersion is non-uniform；
(3) present invention solves when being directly mixed in graphene in nano-cellulose film that graphene dispersion is non-uniform to ask
Topic；
(4) present invention uses vitamin C in-situ reducing graphene oxide compared with other reducing agent (hydroiodic acid, hydrochloric acid, hydrogen fluorine
Acid, glyoxalic acid etc.) it is more environmentally protective, product is more easy to obtain the favor of consumer；
(5) present invention is that nano silver-graphene oxide-nano cellulose composite film is put into reducing agent and is restored, will not
Cause silver ion problems of dissolution.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
The shield effectiveness of product prepared by following embodiment is measured according to standard GB/T/T 30142-2013；Suppression
Bacterium effect is measured according to professional standard QB/T 2738-2012.Tensile strength according to foreign standard JIS P8113-1998 into
Row measures, and elasticity modulus is measured according to standard GB/T/T 11718.8-1989.
The nano-cellulose dispersion liquid used in following embodiment is made by Tempo oxidizing process.Preparation process is as follows：8g
(oven dry stock) → plus deionized water → 1% starches dense → 500rpm is continuously stirred → and adds 0.128gTEMPO (every gram of oven dry stock adds
0.016g TEMPO), (about 48mmol, every gram is absolutely by 0.8g NaBr (every gram of oven dry stock adds 0.1g NaBr) → plus 80mL NaClO
Dry pulp adds in 6mmolNaClO) → stirring → measure reaction pH (as oxidation reaction carries out, pH declines) → addition 0.5mol/L
NaOH → pH 10~10.5 → pH maintain 10 (reaction terminates) → addition 5mL absolute ethyl alcohols terminate reaction → filtration washing →
Wet pulp (5~8 DEG C storage) → plus water after TEMPO oxidations are sized mixing dense → 1% slurry, 5 times → nanofiber of dense → high-pressure homogeneous processing
Plain dispersion liquid.The dimensional parameters of nano-cellulose：Diameter 10nm-50nm, length 10nm-200nm.
The graphene oxide used in following embodiment is made by improved Hummers methods.Preparation process is as follows：In ice water
The reaction bulb of 500mL is assembled in bath, 5g graphite powders and 5g sodium nitrate with the 200mL concentrated sulfuric acids are uniformly mixed, are added with stirring
25g potassium hyperchlorates, after uniform, then score time adds in 15g potassium permanganate, and control temperature is no more than 20 DEG C, after stirring a period of time,
Ice bath is removed, reaction bulb is transferred on magnetic stirrer, electromagnetic agitation continues for 24 hours.Later, it is slowly added to 200mL under stirring
Deionized water, temperature are increased to 98 DEG C or so, after stirring 20min, add in appropriate hydrogen peroxide and restore remaining oxidant, make solution
Become glassy yellow.Then graphite oxide suspension is centrifuged with 10000rpm rotating speeds by several times, and successively with 5%HCl solution and
Deionized water is washed until separating liquid pH=7.Obtained filter cake is dried in vacuo up to graphite oxide.Graphite oxide is ground,
It weighs 300mg to be scattered in 60ml deionized waters, obtains the suspension of brown color, stable glue is obtained after ultrasonic disperse 1h and is hanged
Supernatant liquid.It is then transferred into four-hole boiling flask, adds in 600mg sodium borohydrides and 50mg neopelexes, be warming up to 80 DEG C,
It centrifuges, is washed successively with acetone and deionized water to pH=7, the filter cake vacuum that will be obtained after reflux 16h on this condition
It is saved backup after drying.
Embodiment 1
(1) graphene oxide is prepared using Hummers methods, by drying, dispersion, is dissolved in deionized water and obtains 400mL
2.0mg/mL graphene oxide dispersions；Graphene oxide individual layer rate wherein obtained is 70%~80%, and piece diameter is 100nm
~200nm, thickness in monolayer are 0.8nm~1.0nm；
(2) 10mg nano silvers (grain size of nano silver is 25~50nm) are added to the above-mentioned graphene oxide dispersions of 25mL
In and stir 1h (300~350r/min), obtain finely dispersed nano silver-graphene oxide dispersion；
(3) whole nano silver-graphene oxide dispersions that step (2) obtains are added to 1000g mass fractions is
In 0.1% nano-cellulose dispersion liquid and 2~3h (300~350r/min) is stirred, obtains finely dispersed nano silver-oxidation stone
Black alkene-nano-cellulose dispersion liquid；
(4) dispersion liquids whole obtained by step (3) under 400w ultrasound conditions are vibrated into 40min, and formed a film through vacuum filtration,
The film material for filtering and obtaining is taken out, upper and lower surface is covered with polytetrafluoroethylene (PTFE) processing release paper, is placed in 2 pieces of clean glass plates
Between, it is dried for 24 hours in the environment for being 60 DEG C in temperature, obtains nano silver-graphene oxide-nano-cellulose film；
(5) nano silver-graphene oxide-nano-cellulose film is put in the 8mg/mL vitamin c solutions of 62.5mL instead
1h is answered, reaction temperature is 50 DEG C, pours out vitamin c solution, and dry 2h, obtains nanometer in the environment for being 60 DEG C in temperature by film
Silver-graphene-nano-cellulose film.
1 test result 1 of table
Note：(1) pure nano-cellulose membrane preparation method：The nano-cellulose dispersion liquid that 1000g mass fractions are 1% is passed through
Vacuum filtration film forming is taken out and filters obtained film material, and upper and lower surface is covered with polytetrafluoroethylene (PTFE) processing release paper, be placed in 2 pieces it is clean
Among net glass plate, dried for 24 hours in the environment for being 60 DEG C in temperature, obtain pure nano-cellulose film.
(2) graphene-nano-cellulose membrane preparation method：The graphene oxide dispersion of 25mL concentration 2.0mg/mL is fallen
Enter to 1000g mass fractions in 1% nano-cellulose dispersion liquid and to stir 2~3h, obtain finely dispersed graphene oxide-
Nano-cellulose dispersion liquid；Gained whole dispersion liquid vibrates 40min under 400w ultrasound conditions, and forms a film through vacuum filtration, takes
Going out and filter obtained film material, upper and lower surface is covered with polytetrafluoroethylene (PTFE) processing release paper, is placed among 2 pieces of clean glass plates,
Drying for 24 hours, obtains graphene oxide-nano-cellulose film in the environment for being 60 DEG C in temperature；By graphene oxide-nanofiber
Plain film, which is put in the 8mg/mL vitamin c solutions of 625mL, reacts 1h, and reaction temperature is 50 DEG C, vitamin c solution is poured out, in temperature
Dry 2h in the environment for 60 DEG C is spent, obtains graphene-nano-cellulose film.
Embodiment 2
(1) graphene oxide is prepared using Hummers methods, by drying, dispersion, is dissolved in deionized water and obtains 400mL
1.0mg/mL graphene oxide dispersions；Graphene oxide individual layer rate wherein obtained is 70%~80%, and piece diameter is 100nm
~200nm, thickness in monolayer are 0.8nm~1.0nm；
(2) 1mg nano silvers (grain size of nano silver is 25~50nm) are added to the 1.0mg/mL of the above-mentioned preparations of 100mL
In graphene oxide dispersion and 1h (300~350r/min) is stirred, obtains finely dispersed nano silver-graphene oxide dispersion
Liquid；
(3) whole nano silver-graphene oxide dispersions are added to 100g mass fractions for 1% nano-cellulose to disperse
In liquid and 2~3h (300~350r/min) is stirred, obtains finely dispersed nano silver-graphene oxide-nano-cellulose dispersion
Liquid；
(4) dispersion liquids whole obtained by step (3) under 400w ultrasound conditions are vibrated into 60min, and formed a film through vacuum filtration,
The film material for filtering and obtaining is taken out, upper and lower surface is covered with polytetrafluoroethylene (PTFE) processing release paper, is placed in 2 pieces of clean glass plates
Between, it is dried for 24 hours in the environment for being 60 DEG C in temperature, obtains nano silver-graphene oxide-nano-cellulose film；
(5) nano silver-graphene oxide-nano-cellulose film is put in the 8mg/mL vitamin c solutions of 62.5mL instead
4h is answered, reaction temperature is 50 DEG C, pours out vitamin c solution, and dry 2h, obtains nano silver-stone in the environment for being 60 DEG C in temperature
Black alkene-nano-cellulose film.
2 test result 2 of table
Note：(1) pure nano-cellulose membrane preparation method：100g mass fractions is true for 1% nano-cellulose dispersion liquid warp
Sky filters film forming, takes out the film material for filtering and obtaining, and upper and lower surface is covered with polytetrafluoroethylene (PTFE) processing release paper, is placed in 2 pieces of cleanings
Glass plate among, in temperature is 60 DEG C of environment it is dry for 24 hours, obtain pure nano-cellulose film.
(2) graphene-nano-cellulose membrane preparation method：By the graphene oxide dispersion of 100mL concentration 1.0mg/mL
It is poured into 100g mass fractions to be in 1% nano-cellulose dispersion liquid and stir 2~3h, obtains finely dispersed graphite oxide
Alkene-nano-cellulose dispersion liquid；Gained whole dispersion liquid vibrates 40min under 400w ultrasound conditions, and forms a film through vacuum filtration,
The film material for filtering and obtaining is taken out, upper and lower surface is covered with polytetrafluoroethylene (PTFE) processing release paper, is placed in 2 pieces of clean glass plates
Between, it is dried for 24 hours in the environment for being 60 DEG C in temperature, obtains graphene oxide-nano-cellulose film；By graphene oxide-nanometer
Cellulose membrane, which is put in the 8mg/mL vitamin c solutions of 62.5mL, reacts 4h, and reaction temperature is 50 DEG C, pours out vitamin c solution,
Dry 2h, obtains graphene-nano-cellulose film in the environment for being 60 DEG C in temperature.
Embodiment 3
(1) graphene oxide is prepared using Hummers methods, by drying, dispersion, is dissolved in deionized water and obtains 400mL
1.0mg/mL graphene oxide dispersions；Graphene oxide individual layer rate wherein obtained is 50%~60%, and piece diameter is 100nm
~1 μm, thickness in monolayer is 0.8nm~1.2nm；
(2) 1mg nano silvers (grain size of nano silver is 50~100nm) are added to the above-mentioned graphene oxides of 100mL to disperse
In liquid and 1h (300~350r/min) is stirred, obtains finely dispersed nano silver-graphene oxide dispersion；
(3) mass fraction that whole nano silver-graphene oxide dispersions are added to 100g is 1% nano-cellulose point
In dispersion liquid and 2~3h (300~350r/min) is stirred, obtains finely dispersed nano silver-graphene oxide-nano-cellulose point
Dispersion liquid；
(4) dispersion liquids whole obtained by step (3) under 400w ultrasound conditions are vibrated into 60min, and formed a film through vacuum filtration,
The film material for filtering and obtaining is taken out, upper and lower surface is covered with polytetrafluoroethylene (PTFE) processing release paper, is placed in 2 pieces of clean glass plates
Between, it is dried for 24 hours in the environment for being 60 DEG C in temperature, obtains nano silver-graphene oxide-nano-cellulose film；
(5) nano silver-graphene oxide-nano-cellulose film is put in the 8mg/mL vitamin c solutions of 62.5mL instead
4h is answered, reaction temperature is 50 DEG C, pours out vitamin c solution, and dry 2h, obtains nano silver-stone in the environment for being 60 DEG C in temperature
Black alkene-nano-cellulose film.
3 test result 3 of table
Note：(1) pure nano-cellulose membrane preparation method：100g mass fractions is true for 1% nano-cellulose dispersion liquid warp
Sky filters film forming, takes out the film material for filtering and obtaining, and upper and lower surface is covered with polytetrafluoroethylene (PTFE) processing release paper, is placed in 2 pieces of cleanings
Glass plate among, in temperature is 60 DEG C of environment it is dry for 24 hours, obtain pure nano-cellulose film.
(2) graphene-nano-cellulose membrane preparation method：By the graphene oxide dispersion of 100mL concentration 1.0mg/mL
It is poured into 100g mass fractions to be in 1% nano-cellulose dispersion liquid and stir 2~3h, obtains finely dispersed graphite oxide
Alkene-nano-cellulose dispersion liquid；Gained whole dispersion liquid vibrates 40min under 400w ultrasound conditions, and forms a film through vacuum filtration,
The film material for filtering and obtaining is taken out, upper and lower surface is covered with polytetrafluoroethylene (PTFE) processing release paper, is placed in 2 pieces of clean glass plates
Between, it is dried for 24 hours in the environment for being 60 DEG C in temperature, obtains graphene oxide-nano-cellulose film；By graphene oxide-nanometer
Cellulose membrane, which is put in the 8mg/mL vitamin c solutions of 62.5mL, reacts 4h, and reaction temperature is 50 DEG C, pours out vitamin c solution,
Dry 2h, obtains graphene-nano-cellulose film in the environment for being 60 DEG C in temperature.
Embodiment 4
(1) graphene oxide is prepared using Hummers methods, by drying, dispersion, is dissolved in deionized water and obtains 400mL
2.0mg/mL graphene oxide dispersions；Graphene oxide individual layer rate wherein obtained is 10%~30%, and piece diameter is>
200nm, thickness in monolayer are>1.0nm；
(2) by 10mg nano silvers, (grain size of nano silver is>It 100nm) is added in the above-mentioned graphene oxide dispersions of 25mL
And 1h (300~350r/min) is stirred, obtain finely dispersed nano silver-graphene oxide dispersion；
(3) whole nano silver-graphene oxide dispersions that step (2) obtains are added to 1000g mass fractions is
In 0.1% nano-cellulose dispersion liquid and 2~3h (300~350r/min) is stirred, obtains finely dispersed nano silver-oxidation stone
Black alkene-nano-cellulose dispersion liquid；
(4) dispersion liquids whole obtained by step (3) under 400w ultrasound conditions are vibrated into 40min, and formed a film through vacuum filtration,
The film material for filtering and obtaining is taken out, upper and lower surface is covered with polytetrafluoroethylene (PTFE) processing release paper, is placed in 2 pieces of clean glass plates
Between, it is dried for 24 hours in the environment for being 60 DEG C in temperature, obtains nano silver-graphene oxide-nano-cellulose film；
(5) nano silver-graphene oxide-nano-cellulose film is put in the 8mg/mL vitamin c solutions of 62.5mL instead
1h is answered, reaction temperature is 50 DEG C, pours out vitamin c solution, and dry 2h, obtains nanometer in the environment for being 60 DEG C in temperature by film
Silver-graphene-nano-cellulose film.
4 test result 4 of table
Note：(1) pure nano-cellulose membrane preparation method：The nano-cellulose dispersion liquid that 1000g mass fractions are 1% is passed through
Vacuum filtration film forming is taken out and filters obtained film material, and upper and lower surface is covered with polytetrafluoroethylene (PTFE) processing release paper, be placed in 2 pieces it is clean
Among net glass plate, dried for 24 hours in the environment for being 60 DEG C in temperature, obtain pure nano-cellulose film.
(2) graphene-nano-cellulose membrane preparation method：The graphene oxide dispersion of 25mL concentration 2.0mg/mL is fallen
Enter to 1000g mass fractions in 1% nano-cellulose dispersion liquid and to stir 2~3h, obtain finely dispersed graphene oxide-
Nano-cellulose dispersion liquid；Gained whole dispersion liquid vibrates 40min under 400w ultrasound conditions, and forms a film through vacuum filtration, takes
Going out and filter obtained film material, upper and lower surface is covered with polytetrafluoroethylene (PTFE) processing release paper, is placed among 2 pieces of clean glass plates,
Drying for 24 hours, obtains graphene oxide-nano-cellulose film in the environment for being 60 DEG C in temperature；By graphene oxide-nanofiber
Plain film, which is put in the 8mg/mL vitamin c solutions of 12.5mL, reacts 1h, and reaction temperature is 50 DEG C, vitamin c solution is poured out, in temperature
Dry 2h in the environment for 60 DEG C is spent, obtains graphene-nano-cellulose film.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of plant nanometer cellulose base flexible electromagnetic shielding film, which is characterized in that include the following steps：
(1) raw material nano silver, graphene oxide and nano-cellulose dispersion liquid are taken, with solvent prepare finely dispersed nano silver-
Graphene oxide-nano-cellulose dispersion liquid；Wherein nano silver gross mass is the 1%~20% of graphene oxide gross mass, oxygen
Graphite alkene gross mass is the 5%~10% of nano-cellulose gross mass；The solvent for water, methanol, ethyl alcohol, ethylene glycol,
One or more of glycerine, butanol or n-amyl alcohol；
(2) film forming will be filtered by vacuum after step (1) the dispersion liquid ultrasound deaeration, obtained after dry nano silver-graphene oxide-
Nano cellulose composite film；
(3) step (2) nano silver-graphene oxide-nano cellulose composite film with vitamin C is restored, obtains nanometer
Silver-graphene-nano cellulose composite film, that is, plant nanometer cellulose base flexible electromagnetic shielding film.
2. a kind of preparation method of plant nanometer cellulose base flexible electromagnetic shielding film according to claim 1, feature
It is, the nano silver grain size is 25~100nm.
3. a kind of preparation method of plant nanometer cellulose base flexible electromagnetic shielding film according to claim 2, feature
It is, the grain size of the nano silver is 25~50nm.
4. a kind of preparation method of plant nanometer cellulose base flexible electromagnetic shielding film according to claim 1, feature
Be, the graphene oxide individual layer rate be 50%~80%, piece diameter be 100nm~1 μm, thickness in monolayer for 0.8nm~
1.2nm。
5. a kind of preparation method of plant nanometer cellulose base flexible electromagnetic shielding film according to claim 4, feature
Be, the graphene oxide individual layer rate be 70%~80%, piece diameter be 100nm~200nm, thickness in monolayer for 0.8nm~
1.0nm。
6. a kind of preparation method of plant nanometer cellulose base flexible electromagnetic shielding film according to claim 1, feature
Be, step (1) the specific steps are：
(a) graphene oxide is disperseed with solvent, then nano silver is added in graphene oxide dispersion and stirred to get
Finely dispersed nano silver-graphene oxide dispersion；
(b) finely dispersed nano silver-graphene oxide dispersion that step (a) obtains is mixed with nano-cellulose dispersion liquid
And stir to get finely dispersed nano silver-graphene oxide-nano-cellulose dispersion liquid.
7. a kind of preparation method of plant nanometer cellulose base flexible electromagnetic shielding film according to claim 1, feature
It is, the supersonic frequency of step (2) the ultrasonic deaeration is 300~400w, 15~60min of time.
8. a kind of preparation method of plant nanometer cellulose base flexible electromagnetic shielding film according to claim 1, feature
It is, vitamin C quality is 5~10 times of graphene oxide quality in step (3), and reduction reaction temperature is 40~60 DEG C, instead
It is 1~5h between seasonable.
9. a kind of plant nanometer cellulose base flexible electromagnetic shielding film, which is characterized in that as described in any one of claim 1~8
The preparation method of plant nanometer cellulose base flexible electromagnetic shielding film a kind of be made.
10. a kind of plant nanometer cellulose base flexible electromagnetic shielding film described in claim 9 is in electromagnetic shielding clothes are prepared
Using.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108962619A (en) * | 2018-07-15 | 2018-12-07 | 重庆文理学院 | A kind of laminated film and preparation method thereof for flexible electrode |
| CN109102919A (en) * | 2018-08-24 | 2018-12-28 | 山东圣泉新材料股份有限公司 | A kind of composite conductive film and its preparation method and application |
| CN111574738A (en) * | 2020-05-28 | 2020-08-25 | 青岛科技大学 | Preparation method of nano cellulose based bionic heterogeneous membrane material |
| CN111910420A (en) * | 2020-03-24 | 2020-11-10 | 贵州大学 | Method for preparing thin high-strength composite heat-conducting functional film with sandwich structure |
| CN112500609A (en) * | 2020-11-04 | 2021-03-16 | 国际竹藤中心 | Light high-strength cellulose nanocrystalline/graphene composite film and preparation method thereof |
| CN113772661A (en) * | 2021-10-29 | 2021-12-10 | 浙江理工大学 | Preparation method of reduced graphene oxide/nano-silver composite film |
| CN116554556A (en) * | 2023-05-06 | 2023-08-08 | 华南理工大学 | Cellulose nanocrystalline-reduced graphene oxide composite membrane and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104399998A (en) * | 2014-10-22 | 2015-03-11 | 苏州正业昌智能科技有限公司 | Preparation method of graphene/nano-silver composite material |
| CN105860143A (en) * | 2016-05-14 | 2016-08-17 | 上海大学 | Flexible nanocellulose-graphene composite membrane and preparation method thereof |
| CN106045515A (en) * | 2016-06-01 | 2016-10-26 | 斯迪克新型材料（江苏）有限公司 | Preparation method of graphene-polyimide composite heat conducting film |
| CN107381544A (en) * | 2017-06-16 | 2017-11-24 | 中国科学院福建物质结构研究所 | A kind of graphene film and its preparation method and application |
-
2017
- 2017-12-14 CN CN201711338781.5A patent/CN108219179A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104399998A (en) * | 2014-10-22 | 2015-03-11 | 苏州正业昌智能科技有限公司 | Preparation method of graphene/nano-silver composite material |
| CN105860143A (en) * | 2016-05-14 | 2016-08-17 | 上海大学 | Flexible nanocellulose-graphene composite membrane and preparation method thereof |
| CN106045515A (en) * | 2016-06-01 | 2016-10-26 | 斯迪克新型材料（江苏）有限公司 | Preparation method of graphene-polyimide composite heat conducting film |
| CN107381544A (en) * | 2017-06-16 | 2017-11-24 | 中国科学院福建物质结构研究所 | A kind of graphene film and its preparation method and application |
Non-Patent Citations (3)
| Title |
|---|
| SOON WEI CHOOK ET AL.: "Antibacterial hybrid cellulose-graphene oxide nanocomposite immobilized with silver nanoparticles", 《THE ROYAL SOCIETY OF CHEMISTRY》 * |
| 付长璟: "《石墨烯的制备、结构及应用》", 30 June 2017, 哈尔滨工业大学出版社 * |
| 吴宗山 等: "纳米银的抗菌机理研究进展", 《化工进展》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108962619A (en) * | 2018-07-15 | 2018-12-07 | 重庆文理学院 | A kind of laminated film and preparation method thereof for flexible electrode |
| CN109102919A (en) * | 2018-08-24 | 2018-12-28 | 山东圣泉新材料股份有限公司 | A kind of composite conductive film and its preparation method and application |
| CN111910420A (en) * | 2020-03-24 | 2020-11-10 | 贵州大学 | Method for preparing thin high-strength composite heat-conducting functional film with sandwich structure |
| CN111574738A (en) * | 2020-05-28 | 2020-08-25 | 青岛科技大学 | Preparation method of nano cellulose based bionic heterogeneous membrane material |
| CN112500609A (en) * | 2020-11-04 | 2021-03-16 | 国际竹藤中心 | Light high-strength cellulose nanocrystalline/graphene composite film and preparation method thereof |
| CN113772661A (en) * | 2021-10-29 | 2021-12-10 | 浙江理工大学 | Preparation method of reduced graphene oxide/nano-silver composite film |
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