CN105111605B - High molecular nanometer laminated film and preparation method thereof - Google Patents
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Abstract
The invention discloses a kind of high molecular nanometer laminated film and preparation method thereof.The high molecular nanometer laminated film includes macromolecule matrix and the nano metal material and ionic liquid that are scattered in macromolecule matrix.Preparation method include (1) by nano metal material ultrasonic disperse in ionic liquid, obtain the first dispersion liquid；(2) by high polymer material ultrasonic disperse in organic solvent, the second dispersion liquid is obtained；(3) first and second dispersion liquid is mixed；(4) mixed liquor is spun on substrate, secure satisfactory grades sub- nano compound film.Nano-particle is uniformly dispersed, without secondary agglomeration phenomenon in the high molecular nanometer laminated film of the present invention, and preparation method is simple, with short production cycle, cost is cheap.
Description
Technical field
The invention belongs to macromolecule membrane to prepare and nanochemistry technical field, and in particular to a kind of high molecular nanometer is compound
Film and preparation method thereof.
Background technology
Nano material is a study hotspot in recent years, some special effectses that it has, such as skin effect, small size
Effect, quantum size effect, macro quanta tunnel effect etc. so that nano material is in mechanical property, magnetic performance, calorifics
Energy, optical property, electric property and chemistry and catalytic performance etc., there is the unrivaled characteristic of other materials.
Nano composite material be using matrixes such as resin, rubber, ceramics or metals as continuous phase, with the metal of nano-scale,
The modifying agent such as semiconductor, rigid particles or other inorganic particulates, fiber, CNT is dispersed phase, passes through appropriate preparation side
Modifying agent uniformity is scattered in matrix material by method, forms the compound system that a phase contains nano-sized materials.
Ionic liquid due to extremely low vapour pressure, higher heat endurance and adjustable solvability by as one kind
Substitute the green medium of traditional volatile organic solvent and be widely used in the fields such as organic synthesis, separating-purifying.Due to from
Sub- liquid coordination ability is low, interfacial tension and interface can be small and they easily form hydrogen bonds and have higher order, makes them
Medium, which is can not only be used for, in prepared by the nano material of special appearance plays a part of template again.Therefore the research nothing of ionic liquid
There is particularly important meaning by scientific basis research or practical application.
With the development of nanometer technology, the method for preparing high molecular nanometer laminated film is more and more.But due to nanometer
The grain small surface atom ratio of granularity is big, specific surface area is very big, surface energy is big, in energy unstable state, easily reunites one
Rise, it is difficult to be equably dispersed in the form of nano particle in polymer matrix.Currently, in the system of high molecular nanometer laminated film
It is standby with application field, an existing technological difficulties be prevent nano particle prepare with dispersion process in agglomeration traits,
This is also a hot urgently to be resolved hurrily in current nanotechnology research field.
The content of the invention
The technical problem to be solved in the present invention is overcome the deficiencies in the prior art, there is provided a kind of nano-particle is uniformly dispersed,
High molecular nanometer laminated film without secondary agglomeration phenomenon, also provides that a kind of reaction condition is gentle, technological process is simple, production week
The preparation method for the high molecular nanometer laminated film that phase is short, cost is cheap.
In order to solve the above technical problems, the present invention uses following technical scheme.
A kind of high molecular nanometer laminated film, the high molecular nanometer laminated film include macromolecule matrix and are scattered in institute
State the nano metal material and ionic liquid in macromolecule matrix.
In above-mentioned high molecular nanometer laminated film, it is preferred that the nano metal material is receiving with empty d, f track
Rice metal material, the nano metal material include copper nanoparticle, nano-silver powder, nano-gold powder, nanometer iron powder, nano zinc powder,
One or more in nano-nickel powder；The ionic liquid is the imidazole type ion liquid with lone pair electrons, the ionic liquid
Body includes [emim] BF4、[emim]PF6In one or more.
In above-mentioned high molecular nanometer laminated film, it is preferred that the macromolecule matrix includes polystyrene, poly- methyl-prop
One or more in e pioic acid methyl ester, polyethylene, polyaniline, polyacetylene, polypyrrole, polythiophene.
The technical concept total as one, the present invention also provide a kind of preparation method of high molecular nanometer laminated film, wrap
Include following steps：
(1) by nano metal material ultrasonic disperse in ionic liquid, the first dispersion liquid is obtained；
(2) by high polymer material ultrasonic disperse in organic solvent, the second dispersion liquid is obtained；
(3) the first dispersion liquid is mixed with the second dispersion liquid, through ultrasonic disperse, obtains mixed liquor；
(4) mixed liquor is spun on substrate, obtains high molecular nanometer laminated film.
In the preparation method of above-mentioned high molecular nanometer laminated film, it is preferred that in the step (1), the nanogold
The mass volume ratio for belonging to material and ionic liquid is 1mg~2mg: 5mL~10mL.
In the preparation method of above-mentioned high molecular nanometer laminated film, it is preferred that in the step (1), the nanogold
Category material is the nano metal material with empty d, f track, and the nano metal material includes copper nanoparticle, nano-silver powder, received
One or more in rice bronze, nanometer iron powder, nano zinc powder, nano-nickel powder；The ionic liquid is with lone pair electrons
Imidazole type ion liquid, the ionic liquid include [emim] BF4、[emim]PF6In one or more.
In the preparation method of above-mentioned high molecular nanometer laminated film, it is preferred that in the step (1), the nanogold
Category material ultrasonic disperse is carried out in the process of ionic liquid under inert gas shielding.
In the preparation method of above-mentioned high molecular nanometer laminated film, it is preferred that in the step (2), the macromolecule
The mass ratio of material and organic solvent is 5%~10%.
In the preparation method of above-mentioned high molecular nanometer laminated film, it is preferred that in the step (2), the macromolecule
Material includes one kind in polystyrene, polymethyl methacrylate, polyethylene, polyaniline, polyacetylene, polypyrrole, polythiophene
It is or a variety of；The organic solvent includes the one or more in dichloromethane, chloroform, acetone.
In the preparation method of above-mentioned high molecular nanometer laminated film, it is preferred that in the step (3), described first point
The mass ratio of dispersion liquid and the second dispersion liquid is 1%~5%.
In the present invention, the average grain diameter of the nano metal material is preferably 10nm~30nm.
The invention provides a kind of preparation method of high molecular nanometer laminated film, the film is by nano-particle, ion
Liquid, macromolecule and solvent are prepared, such as Cu/ [emim] BF4/ PS films, Cu/ [emim] BF4/ PMMA films, main profit
Homogeneous nanoparticle sol (such as [emim] BF is made in ionic liquid and nano-particle with ultrasonic disperse technology4- Cu) conduct
The carrier of dispersing nanoparticles, it is distributed in macromolecule matrix (PMMA of such as polarity or nonpolar PE) and is made finely dispersed
High molecular nanometer laminated film, for metallic particles with being not in secondary agglomeration phenomenon in macromolecule recombination process, the technology can
For preparing the dispersed of nano-particle material in the high molecular nanometer laminated films such as conductive, optics and antibacterial, for example, can
So that the electrical conductivity of PE and PMMA based high molecular films increases by 5 orders of magnitude.
Compared with prior art, the advantage of the invention is that：
(1) present invention uses ionic liquid as dispersant, can be small and easy using ionic liquid interfacial tension and interface
Form hydrogen bond and the higher order that has increases the decentralization of nano-particle, reduce the reunion of nano-particle, make nanogold
Metal particles ultrasonic disperse forms relatively stable colloidal sol.
(2) present invention uses PMMA, and PS Polymer materials are film-made stable performance, can prepare has as matrix material
The high molecular nanometer laminated film of the properties such as conductance, optics and antibacterial.
(3) present invention utilizes homemade [emim] BF4- Cu nanoparticle sols reach scattered nanometer as a component
The effect of metallic particles, nano-metal particle is set to be uniformly dispersed in high molecular nanometer laminated film.
(4) preparation method reaction condition of the invention is gentle, and technological process is simple, with short production cycle, and cost is cheap, has wide
General application prospect and important realistic meaning.
Brief description of the drawings
Fig. 1 is the preparation flow schematic diagram of high molecular nanometer laminated film in the embodiment of the present invention.
Fig. 2 is gained [emim] BF in the embodiment of the present invention 14The transmission electron microscope photo of-Cu colloidal sols (the first dispersion liquid), mark
Chi is 100nm.
Fig. 3 is gained [emim] BF in the embodiment of the present invention 14The transmission electron microscope photo of-Cu colloidal sols (the first dispersion liquid), mark
Chi is 5nm.
Fig. 4 is [emim] BF used in the embodiment of the present invention 14The ultraviolet spectrogram of ionic liquid.
Fig. 5 is gained [emim] BF in the embodiment of the present invention 14The ultraviolet spectrogram of-Cu colloidal sols (the first dispersion liquid).
Fig. 6 is [emim] BF in the embodiment of the present invention 14- Cu colloidal sols and [emim] BF4The ultraviolet absorptivity of ionic liquid
Poor spectrogram.
Fig. 7 is [emim] BF used in the embodiment of the present invention 14Ionic liquid and gained [emim] BF4(first point of-Cu colloidal sols
Dispersion liquid) infrared spectrum comparison diagram.
Fig. 8 is copper nanoparticle in the embodiment of the present invention 1 in [emim] BF4Dispersion mechanism schematic diagram in ionic liquid.
Fig. 9 is gained Cu/ [emim] BF in the embodiment of the present invention 14The stereoscan photograph of/PMMA films.
Figure 10 is gained Cu/ [emim] BF in the embodiment of the present invention 24The stereoscan photograph of/PS films.
Figure 11 is the embodiment of the present invention 1 gained Cu/ [emim] BF4/ PMMA films and embodiment 2 gained Cu/ [emim] BF4/
The electrical conductivity of PS films and [emim] BF4The graph of a relation of-Cu colloidal sols (the first dispersion liquid) addition.
Embodiment
Below in conjunction with Figure of description and specific preferred embodiment, the invention will be further described, but not therefore and
Limit the scope of the invention.
Material and instrument employed in following examples are commercially available.
Embodiment 1：
A kind of high molecular nanometer laminated film of the invention, including polymethylmethacrylate matrix (i.e. PMMA matrixes) and
The nanometer Cu and [emim] BF being scattered in PMMA matrixes4(molecular formula is as shown in formula I), i.e. the high molecular nanometer laminated film have
Body is Cu/ [emim] BF4/ PMMA films.
A kind of preparation method of the high molecular nanometer laminated film of above-mentioned the present embodiment, flow is referring to Fig. 1, including following step
Suddenly：
(1) electronic balance weighing 1mg copper nanoparticles are used, the average grain diameter of copper nanoparticle is 10nm~30nm, is added to
10mL[emim]BF4In ionic liquid, under conditions of isolation air, argon gas protection, ultrasonic disperse 2h, make it well mixed,
The first dispersion liquid is obtained, i.e. [emim] BF4- Cu colloidal sols.
(2) it is added to electronic balance weighing 0.06975g PMMA in 1ml dichloromethane solvent, ultrasonic disperse 2h,
Make it well mixed, obtain the second dispersion liquid.
(3) take the dispersion liquids of 0.02790g first to be added in the second dispersion liquid with electronic balance, ultrasonic disperse 3 hours, make
It is well mixed, obtains mixed liquor；
(4) apply one layer on a sheet glass and remove film, take 200 μ L (200 μ L~300 μ L) are above-mentioned to mix with liquid-transfering gun
Liquid is closed, is placed on spin coating instrument and scribbles on the sheet glass except film, rotating speed 3000r/s, time 60s, obtain uniform Cu/ [emim]
BF4/ PMMA high molecular nanometers laminated film (i.e. composite material film), the stereoscan photograph of the film are as shown in Figure 9.
Characterize：
As shown in Figures 2 and 3, to [emim] BF made from the present embodiment step (1)4- Cu colloidal sols (the first dispersion liquid) enter
Row transmission electron microscope characterizes, and studies the interface interaction of solvent and Nanometer Copper in dispersion.Wherein Fig. 2 scales are 100nm, Fig. 3 marks
Chi is 5nm.Transmission electron microscope picture as shown in Figure 2, which can be seen that Nanometer Copper and be dispersed in the form of granules in ionic liquid, to be formed
Colloidal sol, disperse more uniformly, nanometer Cu average grain diameters are 10nm~30nm.Transmission electron microscope picture as shown in Figure 3 can be seen that out
Obvious striped is showed, fringe spacing 0.31746nm, has illustrated that nanometer Cu particles have polycrystalline structure.Electronic Speculum result table
Bright metallic copper still exists as metallic particles in ionic liquid, and this dispersion is designated as into [emim] BF4-Cu。
As shown in figures 4-6, to [emim] BF used in the present embodiment step (1)4Ionic liquid and gained [emim] BF4-Cu
Colloidal sol carries out ultraviolet spectra sign, and wherein Fig. 4 is [emim] BF4Ultraviolet spectrogram, Fig. 5 is [emim] BF4- Cu ultraviolet light
Spectrogram, Fig. 6 are [emim] BF4- Cu and [emim] BF4The poor spectrogram of ultraviolet absorptivity.By Nanometer Copper through scattered obtained by ultrasonic disperse
The light absorption curve of system, compare and can see with the light absorption curve of pure dispersant：In the poor spectrogram shown in Fig. 6, [emim]
BF4There are 3 new absworption peaks at 247,286 and 409nm in-Cu dispersions.In the pure ionic liquid ultraviolet spectra shown in Fig. 4
In figure, strong absworption peak corresponding to 242nm or so is π → π of imidazoles cation*Caused by (permission), 272nm relatively weak absorbing peak
For π → π*Caused by (prohibiting).[emim] BF shown in Fig. 54- Cu disperse systems, with pure [emim] BF shown in Fig. 44Compared to have compared with
Big difference：Strong absworption peak corresponding to 244nm is still π → π of imidazoles cation*Caused by (permission), but with pure [emim] BF4Phase
Than being because [emim] there occurs red shift+After mating reaction occurs with Cu, Cu electronics is to [emim]+Transition and it is caused.
409nm absworption peak corresponds to Cu d → d electron transitions, and 409nm is purple light, [emim] BF4It is pico- that yellow is presented in-Cu disperse systems
The phenomenon of intensification.Illustrate nanometer Cu and [emim] BF4It is to be combined with a kind of strong coordination, this effect causes the sample
Still it is the light yellow clear liquid of stabilization after placing half a year, and obvious fourth dongle phenomenon is presented.
Fig. 7 is [emim] BF in the embodiment of the present invention 14[emim] BF4- Cu infrared spectrum comparison diagram.As seen from the figure,
3550~3650cm-1Corresponding N-H stretching vibration peak；1550~1650cm-1Corresponding C=C, C=N ring stretching vibration；
755cm-1Left and right corresponds to the absworption peak of B-F keys.Compare [emim] BF4- Cu and [emim] BF4Infrared spectrogram can be seen that
[emim]BF4- Cu is in 3550~3650cm-1Obvious blue shift occurs for wave number section.In imidazole-like ionic liquid, the N on imidazole ring
With H-shaped into hydrogen bond ionic liquid can be made to form network structure.And in [emim] BF4In-Cu systems, on Nanometer Copper and imidazole ring
Coordination weaken the hydrogen bond that N atoms and H atom are formed on ring, destroy the network structure of ionic liquid, so as to there occurs
Blue shift.In addition, 1450~1650cm-1About 1cm occurs for wave number section-1Wave number red shift, it is because copper nanoparticle is in [emim] BF4Ion
After disperseing in liquid, copper and [emim] BF4Intermolecular coordination result in the delocalization of the conjugated electrons on imidazole ring, make imidazoles
The stretching vibration frequency of ring skeleton moves to lower wave number, illustrates Cu and [emim]+Between form stronger coordination.
Fig. 8 is copper nanoparticle in [emim] BF4Dispersion mechanism schematic diagram in ionic liquid.Above-mentioned Fig. 2 to the Fig. 7 of comprehensive analysis
The characterization result of shown transmission electron microscope, ultraviolet spectra and infrared spectrum, the anions and canons and its ion pair of ionic liquid are with receiving
It is a kind of relatively strong interaction more than intermolecular Van der Waals force category between rice copper, this interaction includes [emim]+With
σ coordinate bonds, the interaction of d-p pi bonds between Nanometer Copper, and Nanometer Copper and anion interaction etc..These stronger phases
Interaction can overcome the Van der Waals force and hydrogen bond between Nanometer Copper, avoid the reunion of Nanometer Copper；On the other hand, this interaction
The obvious electronic structure for changing Nanometer Copper is still not enough to, so that the Nanometer Copper being dispersed in ionic liquid can keep its intrinsic
Electronic Performance.
Fig. 9 is gained Cu/ [emim] BF in the embodiment of the present invention 14The stereoscan photograph of/PMMA films.As shown in figure
Scanning electron microscope (SEM) photograph can be seen that in the film obtained by preparation method of the present invention, metal nanoparticle is with ionic liquid
One entirety, and metal nanoparticle is to be homogeneously dispersed in granular form in high molecular polymer, [emim] BF4-Cu
Obvious interface is not present between macromolecule.Electronic Speculum result shows that metal nano copper still exists as metallic particles, with
During polymer-based bluk recombination, there is not increase phenomenon of reuniting again.
Embodiment 2：
A kind of high molecular nanometer laminated film of the invention, including polystyrene matrix (i.e. PS matrixes) and it is scattered in PS bases
Nanometer Cu and [emim] BF in body4(molecular formula is as shown in formula I), i.e., the high molecular nanometer laminated film is specially Cu/
[emim]BF4/ PS films.
A kind of preparation method of the high molecular nanometer laminated film of above-mentioned the present embodiment, comprises the following steps：
(1) electronic balance weighing 1mg copper nanoparticles are used, the average grain diameter of copper nanoparticle is 10nm~30nm, is added to
10mL[emim]BF4In ionic liquid, under conditions of isolation air, argon gas protection, ultrasonic disperse 2h, make it well mixed, obtain
To the first dispersion liquid, i.e. [emim] BF4- Cu colloidal sols.
(2) it is added in 1mL dichloromethane solvent, ultrasonic disperse 2h, is made with electronic balance weighing 0.06975g PS
It is well mixed, obtains the second dispersion liquid.
(3) it is added to the dispersion liquids of electronic balance weighing 0.02790g first in the second dispersion liquid, ultrasonic disperse 3 hours,
Make it well mixed, obtain mixed liquor.
(4) apply one layer on a sheet glass and remove film, take the above-mentioned mixed liquors of 200 μ L with liquid-transfering gun, be placed in spin coating instrument
On sheet glass, rotating speed 3000r/s, time 60s, uniform Cu/ [emim] BF is obtained4/ PS high molecular nanometer laminated films, this is thin
The stereoscan photograph of film is as shown in Figure 10.
Figure 10 is gained Cu/ [emim] BF in the present embodiment 24The stereoscan photograph of/PS films.By the scanning shown in scheming
Electron microscope can be seen that copper nano-particle before this and be uniformly dispersed in ionic liquid, that is, is wrapped in around copper nano-particle
One layer of ionic liquid, is then uniformly dispersed in polystyrene again, [emim] BF4Exist between-Cu and macromolecule obvious
Interface.Compared to embodiment 1, because the polarity of PS and PMMA both polymer-based bottom materials is different, made with different macromolecules
For in the laminated film obtained by base material, [emim] BF4Interface also can be different between-Cu and macromolecule.Electronic Speculum result table
Bright metal nano copper still exists as metallic particles, during with polymer-based bluk recombination, does not occur reuniting again
Increase phenomenon.
Figure 11 is embodiment 1 gained Cu/ [emim] BF4/ PMMA and embodiment 2 gained Cu/ [emim] BF4/ PS Performances of Novel Nano-Porous
The electrical conductivity and [emim] BF of rice composite high-molecular film4The graph of a relation of-Cu additions.[emim]BF4- Cu additions are respectively
0th, 1%, 2%, 3%, 4% and 5%.As seen from the figure, in certain scope, the electrical conductivity of film is with [emim] BF4-
The increase of Cu contents and increase, but the electrical conductivity of different polymer matrix films embodies different changing rules.With PMMA
For matrix when, the electrical conductivity of film is with [emim] BF4The increase of-Cu contents and increase, as [emim] BF4- Cu content is
5%, maximum conductivity is up to 1.029 × 10-2S·cm-1, the electrical conductivity 1.7241 × 10 with pure matrix-7S·cm-1Compare, increase
5 orders of magnitude；When using PS as matrix, the electrical conductivity of film is with [emim] BF4The increase of-Cu contents and in certain model
Interior increase is enclosed, but begins to show the trend successively decreased more than this scope, [emim] BF4- Cu content is 3%, maximum electricity
Conductance is up to 3.4763 × 10-2S·cm-1, the electrical conductivity 1.7241 × 10 with pure matrix-7S·cm-1Compare, add 5 quantity
Level.
Described above is only the preferred embodiment of the present invention, and protection scope of the present invention is not limited merely to above-mentioned implementation
Example.All technical schemes belonged under thinking of the present invention belong to protection scope of the present invention.It is noted that for the art
Those of ordinary skill for, improvements and modifications under the premise without departing from the principles of the invention, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (4)
1. a kind of high molecular nanometer laminated film, it is characterised in that the high molecular nanometer laminated film includes macromolecule matrix
With the nano metal material and ionic liquid being scattered in the macromolecule matrix；
The nano metal material is the nano metal material with empty d, f track, and the nano metal material includes Nanometer Copper
One or more in powder, nano-silver powder, nano-gold powder, nanometer iron powder, nano zinc powder, nano-nickel powder；The ionic liquid is
Imidazole type ion liquid with lone pair electrons, the ionic liquid include [emim] BF4、[emim]PF6In one kind or more
Kind；
The macromolecule matrix is polystyrene, polymethyl methacrylate, polyethylene, polyaniline, polyacetylene, polypyrrole, poly-
One or more in thiophene；
Nano-particle is uniformly dispersed, without secondary agglomeration phenomenon in the high molecular nanometer laminated film, metal nanoparticle with from
Sub- liquid is an entirety, and metal nanoparticle is to be homogeneously dispersed in granular form in high molecular polymer.
2. a kind of preparation method of high molecular nanometer laminated film, comprises the following steps：
（1）By nano metal material ultrasonic disperse in ionic liquid, the first dispersion liquid is obtained；
（2）By high polymer material ultrasonic disperse in organic solvent, the second dispersion liquid is obtained；
（3）First dispersion liquid is mixed with the second dispersion liquid, through ultrasonic disperse, obtains mixed liquor；
（4）Mixed liquor is spun on substrate, obtains high molecular nanometer laminated film；
The step（1）In, the mass volume ratio of the nano metal material and ionic liquid is 1mg~2mg: 5mL~10mL；
The step（1）In, the nano metal material is the nano metal material with empty d, f track, the nano metal
Material includes the one or more in copper nanoparticle, nano-silver powder, nano-gold powder, nanometer iron powder, nano zinc powder, nano-nickel powder；
The ionic liquid is the imidazole type ion liquid with lone pair electrons, and the ionic liquid includes [emim] BF4、[emim]PF6
In one or more；
The step（1）In, the nano metal material ultrasonic disperse is under inert gas shielding in the process of ionic liquid
Carry out；
The step（2）In, the high polymer material is polystyrene, polymethyl methacrylate, polyethylene, polyaniline, poly-
One or more in acetylene, polypyrrole, polythiophene；The organic solvent includes one in dichloromethane, chloroform, acetone
Kind is a variety of；
Nano-particle is uniformly dispersed, without secondary agglomeration phenomenon in the high molecular nanometer laminated film, metal nanoparticle with from
Sub- liquid is an entirety, and metal nanoparticle is to be homogeneously dispersed in granular form in high molecular polymer.
3. the preparation method of high molecular nanometer laminated film according to claim 2, it is characterised in that the step（2）
In, the mass ratio of the high polymer material and organic solvent is 5%~10%.
4. the preparation method of high molecular nanometer laminated film according to claim 2, it is characterised in that the step（3）
In, the mass ratio of first dispersion liquid and the second dispersion liquid is 1%~5%.
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| CN107082889B (en) * | 2017-04-26 | 2019-06-18 | 华中科技大学 | A kind of Centimeter Level, grain polymer grafting gold nanoparticle composite single layer film adjustable in pitch and preparation method thereof |
| CN108485263A (en) * | 2018-04-06 | 2018-09-04 | 菏泽学院 | A kind of conductive, transparent polymer material and preparation method thereof |
| CN108892849A (en) * | 2018-07-18 | 2018-11-27 | 广西南宁荣威德新能源科技有限公司 | A kind of high density polyethylene (HDPE) bilayer feed pipe and preparation method thereof |
| CN109610162B (en) * | 2018-09-30 | 2021-03-16 | 杭州创屹机电科技有限公司 | Cotton-flax antibacterial finishing agent |
| CN109659071B (en) * | 2019-01-21 | 2020-11-27 | 华碳研发(深圳)有限公司 | Flexible composite polymer film containing carbon nano tube and nano silver and preparation method thereof |
| CN111270228A (en) * | 2020-03-10 | 2020-06-12 | 长虹美菱股份有限公司 | Preparation method of inorganic antibacterial coating of antibacterial self-cleaning display screen |
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