CN106297966A - Nesa coating that a kind of metal nanometer line oxidation-resistant material is compound and preparation thereof - Google Patents
Nesa coating that a kind of metal nanometer line oxidation-resistant material is compound and preparation thereof Download PDFInfo
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- CN106297966A CN106297966A CN201610703852.6A CN201610703852A CN106297966A CN 106297966 A CN106297966 A CN 106297966A CN 201610703852 A CN201610703852 A CN 201610703852A CN 106297966 A CN106297966 A CN 106297966A
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- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
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- H—ELECTRICITY
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
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Abstract
The present invention relates to transparency electrode technical field, specifically disclose the nesa coating that a kind of metal nanometer line oxidation-resistant material is compound, the transparent metal nano wire including high conductivity and one layer of continuous film for the oxidation-resistant material of air-isolation in described metal nano wire grid outer side covers；Described oxidation-resistant material is the nano-metal-oxide of Graphene or electric conductivity.The nesa coating product that the metal nanometer line oxidation-resistant material of the present invention is compound, belongs to the transparent conductive film of a new generation, and material source enriches, preparation is relatively easy, low cost, cost performance is high, flexible, nontoxic, resistance to environment, chemical stability is good, is difficult to reduction, and there is the premium properties such as optimal square resistance and light transmittance, and flexibility.
Description
Technical field
The present invention relates to transparency electrode technical field, be specifically related to compound saturating of a kind of metal nanometer line-oxidation-resistant material
Bright conducting film and preparation thereof.
Background technology
Transparent conductive material is the transparent material that a class has electric conductivity function, extensively should at numerous industrial circles
With, such as used in electronic industry transparent antistatic encapsulant, transparent electrode material, electrochromic display material, smart window material, thoroughly
Bright thermo electric material, nonlinear optical material and transparent anti-electromagnetic-radiation material etc..Industrial most widely applied saturating
Bright sull is tin indium oxide (indium tin oxide) thin film, is called for short ito thin film.Ito thin film is to have both light transmission
With a kind of important photoelectric material of electric conductivity, (electricalresistivityρ is about 10 to have good conductivity-4Ω cm), to visible transparent
(transmitance is up to more than 85%), strong to infrared light (reflectance is more than 80%), to microwave attenuation rate more than 85%, and
The good characteristics such as and processing characteristics is good, it is simple to etching, film hardness is high, the most wear-resisting but also resistance to chemical attack.But use ITO to deposit
In many problems, being mainly manifested in following several aspect: first, indium is rare precious metal, and the development of technology brings world's model
The demand enclosed makes it, and supply falls short of demand.Second, its preparation method is much more expensive, and the target such as prepared is up to nearly ten thousand yuan of every public affairs
Jin, sputtering method, to evaporate the preparation methoies such as deposition, pulsed laser deposition extremely complex, and equipment requirements is the highest, needs fine vacuum, height
Accurate stoicheiometry controls and strict oxide structure morphology Control, technology controlling and process difficulty.The oxides such as the 3rd, ITO
Thin film is the crystalline material of a kind of fragility, and applying stress will be damaged, causes its electric conductivity and optical clarity significantly to decline
(electrical conductivity can decline several order of magnitude) and cause and use by considerable restraint, novel touch display screen, flexible display screen and
Have the biggest restriction in the application of other compliant conductive hyaline membranes, this point be all of oxide-base in transparent conductive film all
Some shortcomings.4th, heavy metal indium has toxicity, can be harmful in preparation and application process；Additionally Sn's and In is former
Son amount is relatively big, easily infiltrates into substrate interior, poison backing material in film forming procedure, especially pollutes tight in liquid crystal display device
Use is heavily caused to be restricted.5th, ITO can be reduced in the environment such as hydrogen, and hydrogen be solaode preparation musted
Must, the efficiency of solaode can be reduced after ITO reduction.Therefore its further application development prospect is just led by novel transparent
The challenge of electric material.These a new generation transparent conductive materials include: 1) new oxide transparent conductive material FTO (SnO:F),
AZO, GZO (ZnO:Gd) etc., 2) the organic conductive transparent material 3 such as polythiophene) Graphene, CNT, the nanometer such as nano-silver thread
Transparent conductive film.
Summary of the invention
In view of this, it is necessary to for above-mentioned problem, it is provided that it is transparent that a kind of metal nanometer line-oxidation-resistant material is combined
Conducting film and preparation thereof.
For achieving the above object, the present invention takes following technical scheme:
The nesa coating that the metal nanometer line-oxidation-resistant material of the present invention is compound, including the transparent metal of high conductivity
Nano wire and at one layer of the described metal nano wire grid outer side covers continuous film for the oxidation-resistant material of air-isolation；Institute
State the nano-metal-oxide that oxidation-resistant material is Graphene or electric conductivity.
Further, described metal nanometer line includes: nano silver wire, copper nano-wire, nanowires of gold, palladium nanometer wire, alloy
Nano wire or the copper heart/gold shell, galactic center/gold shell nano wire.
Further, described metal nanometer line average diameter is less than 80 nanometers, and draw ratio is more than 400；Described Graphene 5 layers
Following percentage ratio 70% or more than.
Further, described metal nanometer line average diameter is less than 50 nanometers；The percentage ratio of described Graphene less than 5 layers exists
80% or more than.
Further, described metal nanometer line average diameter is less than 30 nanometers；The percentage ratio of described Graphene less than 5 layers exists
90% or more than.
Further, described nano-metal-oxide includes nano zine oxide and nano-sized iron oxide.
The preparation method of the transparent conductive film that a kind of metal nanometer line-Graphene is compound, including:
Step 1: the preparation of dispersion liquid
(1) the metal nanometer line preparation technology using this area conventional prepares metal nanometer line dispersion liquid, including: metal is twin
The brilliant nano wire selecting crystal face respectively to form relatively big L/D ratio to abnormal shape growth under the protection of organic ligand；
(2) preparation of graphene dispersing solution: use oxidation-reduction method or high speed dispersion method to prepare graphene solution；Described
Graphene solution uses the crystalline graphite powder of 20-200 mesh to prepare, and in graphene solution, the graphene film of less than 5 layers accounts for 70-
90%；
Or use the sol method of this area routine to prepare nano-metal-oxide；
Step 2: substrate is chemically modified
Substrate surface is used strong acid, strong acid and the mixed liquor of strong oxidizer, highly basic hydroxylating or uses at oxygen plasma
Manage after carboxylated or hydroxylating processes, use the coupling agent containing sulfydryl and amino to modify；
Step 3: film
First metal nanometer line dispersion liquid is coated in substrate, is coated oxidation-resistant material that step 1 prepares in upper one-tenth
Film, forms uniform and stable transparent conductive film；The present invention is in order to obtain being firmly combined with stable transparent conductive film, employingization
Learn the method modifying grafting, it is achieved that metal nanometer line, graphene platelet and the chemical bonding of the substrate such as glass, PET.
Step 4: post processing
After coating, use hot steaming method to remove solvent, heating realizes substrate and metal nanometer line, the valence bond of oxidation-resistant material
Close.
Further, substrate described in step 2 is substrate of glass or PET base；For glass basic surface, through strong acid or
After the mixed liquor of strong acid and strong oxidizer processes hydroxylating, modify with mercaptosilane coupling agents and amino silicane coupling agent；
For PET base, after highly basic chemical treatment hydroxylating, use and have the coupling agent of sulfydryl and amino to modify；Chemical modification is adopted
It is grafted the coupling agent got up carries out with can be combined with substrate, metal nanometer line, Graphene or nano-metal-oxide simultaneously
Modify.The nano wires such as Yin Yin easily and sulfydryl combination, graphene planes usually have carboxyl, epoxy radicals and hydroxyl, can and ammonia
The groups such as base are strong to be closed.Coupling agent contains and the conjugated group of the functional coatings such as substrate and nano silver wire Graphene simultaneously, according to not
With coupling agent can realize chemical graft under certain process conditions.
Further, described in step 3 film use wet type precision coating process, including ramp type coating, curtain,
One in slit coating, roll printing, gravure coating process etc..
Further, before the film described in step 3, regulation solution and the surface tension of substrate so that solution is in substrate
On contact angle reduce as far as possible.In the present invention, regulate capillary method depending on the character of substrate and solution, as with ethanol
Or during aqueous solution, substrate surface hydroxylating or mild oxidation (carboxylated) can be made, hydrophilic parent's ethanol can be realized；Such as glass
Glass substrate surface, the mixed liquor hydroxylating through strong acid or strong acid and strong oxidizer processes；PET base, by highly basic chemistry hydroxyl
Baseization processes；Or PET, the carboxylated process of glass oxygen plasma.
The invention have the benefit that
The nesa coating product that the metal nanometer line-oxidation-resistant material of the present invention is compound, belongs to the transparent of a new generation and leads
Conductive film, can overcome the various shortcomings of conventional transparent conductive film, and its material source enriches, and preparation is relatively easy, cost
Low, cost performance is high, flexible, nontoxic, resistance to environment, and chemical stability is good, is difficult to reduction.Metal nanometer line-oxidation-resistant material is multiple
The transparent conductive film closed has the premium properties such as optimal square resistance and light transmittance, and flexibility.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of nano silver wire in embodiment 1.
Detailed description of the invention
For making the object, technical solutions and advantages of the present invention clearer, below in conjunction with the embodiment of the present invention, to this
Bright technical scheme is made the most clearly and completely to describe.It should be noted that described embodiment is only the present invention one
Section Example rather than whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art are not doing
Go out the every other embodiment obtained under creative work premise, broadly fall into the scope of protection of the invention.
Graphene transparent conductive film, square resistance is below 300 ohm, and technique is adjustable, solves Graphene and base
The combination problem at the end, has mechanical stability high, uniformity is high, flexible grade for outstanding advantages, bends 10000 (bending diameters
2mm) electrical conductivity declines less than 2%.
Nano silver wire nesa coating light transmittance more than 92%, square resistance less than 80 ohm, and these performance techniques
Adjustable, mist degree 1.5%, there is mechanical stability high, the outstanding advantages such as uniformity is high, bend 10000 (bending diameter 2mm) electricity
Conductance declines less than 2%.
But nano silver wire film has a following serious shortcoming:
First, the most easily oxidation: Ag+O2→Ag2O
After silver oxidation, resistance significantly becomes big, causes nano silver wire film rectangular resistance unstable, and square resistance becomes big.Warp
Test, the initial square resistance of nano silver wire thin film that we prepare is 50 ohm, under 30 DEG C of pure oxygens, square electricity after 100 hours
Resistive becomes 120 ohm, in 40 DEG C of air, becomes 80 ohm after 600 hours.The instability of square resistance has had a strong impact on Yin Na
The commercial Application of the wire thin film that rice noodle is transparent.
Second, the electrical conduction mechanism of nano silver wire thin film is that nano silver wire forms grid conduction, and it is flat that sizing grid is usually 10
Side's micron, can meet demand when this is for some less demanding application, but owing to nano silver wire thin film is among grid
Being insulating properties, the uniformity that causes conducting electricity is the most careful, shows etc. for OLED and requires that high transparent conductive film is the most inapplicable
?.Copper nano-wire thin film has these problems equally.Gold, palladium nanometer wire, or copper/gold, silver/gold (heart/shell) nano wire film
Non-oxidizability is much higher, but expensive, also has grid conduction the most careful simultaneously.Application copper/gold, silver/gold (heart/shell) is received
Rice noodle thin film maintain and gold, palladium nanometer wire thin film non-oxidizability outside have than gold, the advantage of palladium nanometer wire low cost.
Nano zine oxide prepared by sol method, the sull light transmission such as nano-sized iron oxide is high, non-oxidizability stability
Good, but electric conductivity is very poor, and although thin film electric conductivity prepared by high temperature sputtering method has improvement, but equipment is complicated, and energy consumption is high.
The method generally preparing transparent graphene conductive film is CVD, is prepared into continuous transparent conductive thin film, the method
Presently, there are preparation cost high, complex process, control difficulty, add the outstanding difficultys such as man-hour is easily broken.
Composite transparent conductive film prepared by the method that the present invention takes solution to coat, the method technique is simple, and preparation is easy,
Can directly prepare in substrate, have a continuation handling ease, resistance to oxidation, stability is high, and whole face all conducts electricity that (non-grid is led
Electricity) outstanding advantages.
Additionally, Graphene or the exsertile corrosion-resistant coating of one, graphene film is in addition to hydrogen atom, and other own
Atom, molecule all can not pass through, can effectively internal layer material and surrounding be kept apart.Table 1 is transparent conduction
The performance comparison of the transparent conductive film of thin film and a new generation:
The performance parameter of the different conductive film of table 1
| Electrically conducting transparent film type | ITO | Nano silver wire | Graphene | CNT |
| Square resistance/Ω | 150 | 30-50 | 300 | 400 |
| Light transmittance/% | 88 | 90 | 90 | 88 |
| Color | Pale yellow or shallow palm fibre | Colourless | Colourless | Colourless |
| Resistance to bend(ing) | Difference | Very well | Good | Good |
| Environment resistant | Good | Difference | Good | Good |
| Scale | Good | Good | Good | Good |
The present invention is by metal nanometer line transparent conductive film and transparent graphene conductive film or high light transmittance nano metal
Sull combines, and first prepares suitable substrate, such as PET, glass etc., prepares metal nanometer line transparent in substrate
Conductive film, is then coated with a layer graphene thin slice or high light transmittance metal oxygen on metal nanometer line transparent conductive film
Thin film, forms a layer graphene or transparent conductive metal oxide thin film.Nano silver wire-the Graphene being prepared/
Metal-oxide compound transparent electricity conductive film has both advantages, and overcomes respective shortcoming.There is the low (ratio of square resistance
Nano silver wire transparent conductive film is the lowest), and nano silver wire inside is thin at graphene platelet or nano-metal-oxide
Under the protection of film, with antioxidation, thus the stability of the electrical property of whole transparent conductive film can be maintained again, and conduct electricity
Graphene platelet or nano-metal-oxide are filled with the space between nano silver wire grid, and the point of gap is passed through Graphene
Or nano-metal-oxide and nano silver wire UNICOM get up, it is achieved that the conduction of whole, the careful property of conduction is good.Simultaneously because
Being solution coating process, have technique and the most easily realize, can directly prepare in applicable substrate, post-treatment is easy, therefore
The feasibility that large-scale industrial realizes is the highest.
In addition present invention is alternatively directed to metal nanowire thin-films and solution coating process transparent graphene conductive film processed
In journey, nano silver wire or graphene platelet easily come off, and cause electrical property to decline, post-treatment difficulty, the problems such as yield rate is low,
Substrate (PET, glass etc.) to transparent conductive film has carried out chemical modification, it is achieved that nano silver wire and Graphene or nanometer
The weak Van der Waals force combined between oxide and transparent substrates combines and is changed into strong covalent bond or ionic bond combination so that
The flexible raising of transparent conductive film, buckle resistance increases, and in the course of processing, stability is high, and yield rate and performance can be significantly
Improve.
Embodiment 1
0.1 micromolar AgNO3With 0.1 micromolar copper chloride mixing, add proper amount of glycol and appropriate suitably molecule
The PVP of amount, is heated to 140 DEG C, keeps 40 minutes, i.e. can get diameter 40 nanometer, the nano silver wire of length 18-25 micron.Will
The crystalline graphite powder of 40 mesh adds in aqueous solution, stirs with high speed dispersor, obtains graphene aqueous solution, wherein graphene solution
Middle graphene film less than 5 layers occupy 60-70%.
The PET film of 50 microns, by 20% sodium hydroxide hydroxylating, modifies mercaptosilane coupling agents and amino silicone the most simultaneously
Alkane coupling agent, coats nano silver wire dispersion liquid, 120 DEG C of bakings with spin-coating method (large-area film is also prepared with ramp type rubbing method)
Dry, graphene dispersing solution in spin coating the most again, 180 DEG C process 1 minute, have just obtained nano silver wire Graphene electrically conducting transparent thin
Film.Silver nanoparticle Graphene line composite transparent conductive film square resistance 50 ohm, light transmittance 89%, under 200 DEG C of pure oxygen environments 200
It electrical conductivity declines less than 0.2%, and careful have conductiving point to 1 nanoscale；Bend 10000 (diameter 2mm) electrical conductivity to decline
Less than 2%, mist degree is less than 1.2%.
Embodiment 2
Nano silver wire dispersion liquid is prepared according to the method in embodiment 1.Use concentrated sulphuric acid and potassium permanganate oxidation 50 purpose
Crystalline graphite powder, obtains graphene oxide solution after ultrasonic disperse, becomes graphene solution through hydrazine hydrate reduction.
The flexible glass of 50 microns is hydroxylating after concentrated sulphuric acid and hydrogen peroxide mixed liquor process, then with hydrosulphonyl silane and ammonia
Base silane is modified simultaneously, the most spin-coated method (large area film is also prepared with curtain method, gravure coating process) silver coating
Nanowire dispersion, 120 DEG C process one minute, are then spin coated onto graphene dispersing solution, and 180 DEG C process one minute.Silver nanoparticle graphite
Alkene line compound transparent electricity conductive film square resistance 50 ohm, light transmittance 89%, under 200 DEG C of pure oxygen environments under 200 days electrical conductivity
Fall less than 0.2%, careful have conductiving point to 1 nanoscale；Bend 10000 (diameter 2mm) electrical conductivity and decline less than 2%, mist
Degree is less than 1.2%.
Embodiment 3
Nano silver wire dispersion liquid, outsourcing Zinc oxide nanoparticle colloidal sol, two kinds of dispersions are prepared according to the method in embodiment 1
Liquid mixes.
The flexible glass of 50 microns is hydroxylating after concentrated sulphuric acid and hydrogen peroxide mixed liquor process, with hydrosulphonyl silane and ammonia
Base silane is modified simultaneously, and the most spin-coated method (large area film also can be prepared with curtain method, gravure coating process) is coated with
Nano silver wire and the mixed dispersion liquid of nano zine oxide, 120 DEG C process one minute, and 180 DEG C process one minute, and composite transparent conducts electricity
Film rectangular resistance 50 ohm, light transmittance 92%, under 200 DEG C of pure oxygen environments, electrical conductivity decline less than 0.2% in 200 days, careful
Conductiving point is had to 1 nanoscale；Bending 10000 (diameter 2mm) electrical conductivity and decline less than 2%, mist degree is less than 1.2%.
Embodiment described above only have expressed the several embodiments of the present invention, and it describes more concrete and detailed, but also
Therefore the restriction to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that, for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, it is also possible to make some deformation and improvement, these broadly fall into the guarantor of the present invention
Protect scope.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. the nesa coating that metal nanometer line-oxidation-resistant material is compound, it is characterised in that including: high conductivity saturating
Bright metal nanometer line and in described metal nano wire grid outer side covers the one layer company for the oxidation-resistant material of air-isolation
Continuous film；Described oxidation-resistant material is the nano-metal-oxide of Graphene or electric conductivity.
The nesa coating that metal nanometer line-oxidation-resistant material the most according to claim 1 is compound, it is characterised in that institute
State metal nanometer line to include: nano silver wire, copper nano-wire, nanowires of gold, palladium nanometer wire, alloy nano-wire or the copper heart/gold shell,
Galactic center/gold shell nano wire.
The nesa coating that metal nanometer line-oxidation-resistant material the most according to claim 1 is compound, it is characterised in that institute
State metal nanometer line average diameter and be more than 400 less than 80 nanometers, draw ratio；The percentage ratio of described Graphene less than 5 layers is 70%
More than or.
The nesa coating that metal nanometer line-oxidation-resistant material the most according to claim 3 is compound, it is characterised in that institute
State metal nanometer line average diameter less than 50 nanometers；The percentage ratio of described Graphene less than 5 layers 80% or more than.
The nesa coating that metal nanometer line-oxidation-resistant material the most according to claim 4 is compound, it is characterised in that institute
State metal nanometer line average diameter less than 30 nanometers；The percentage ratio of described Graphene less than 5 layers 90% or more than.
The nesa coating that metal nanometer line-oxidation-resistant material the most according to claim 1 is compound, it is characterised in that institute
State nano-metal-oxide and include nano zine oxide and nano-sized iron oxide.
7. the system of the nesa coating that the metal nanometer line-oxidation-resistant material described in a claim 1-6 any one is combined
Preparation Method, it is characterised in that including:
Step 1: the preparation of dispersion liquid
(1) the metal nanometer line preparation technology using this area conventional prepares metal nanometer line dispersion liquid, including: metal twin exists
The lower nano wire selecting crystal face respectively to form relatively big L/D ratio to abnormal shape growth of the protection of organic ligand；
(2) preparation of graphene dispersing solution: use oxidation-reduction method or high speed dispersion method to prepare graphene solution；Described graphite
Alkene solution uses the crystalline graphite powder of 20-200 mesh to prepare, and in graphene solution, the graphene film of less than 5 layers accounts for 70-90%；
Or use the sol method of this area routine to prepare nano-metal-oxide；
Step 2: substrate is chemically modified
Substrate surface is used strong acid, strong acid and the mixed liquor of strong oxidizer, highly basic hydroxylating or processes carboxylic with oxygen plasma
After base or hydroxylating process, the coupling agent containing sulfydryl and amino is used to modify；
Step 3: film
First metal nanometer line dispersion liquid is coated in substrate, is coated oxidation-resistant material that step 1 prepares in upper film forming, shape
The most stable transparent conductive film；
Step 4: post processing
After coating, use hot steaming method to remove solvent, heating realizes substrate and metal nanometer line, the valence bond conjunction of oxidation-resistant material.
The preparation method of the nesa coating that metal nanometer line-oxidation-resistant material the most according to claim 7 is compound, it is special
Levying and be, substrate described in step 2 is substrate of glass or PET base；For glass basic surface, through strong acid or strong acid and strong oxygen
After the mixed liquor of agent processes hydroxylating, modify with mercaptosilane coupling agents and amino silicane coupling agent；For PET base
The end, after highly basic chemical treatment hydroxylating, use and have the coupling agent of sulfydryl and amino to modify.
The preparation method of the nesa coating that metal nanometer line-oxidation-resistant material the most according to claim 7 is compound, it is special
Levying and be, film described in step 3 uses wet type precision coating process, is coated with including ramp type coating, curtain, slit
One in cloth, roll printing, gravure coating process.
The preparation method of the nesa coating that metal nanometer line-oxidation-resistant material the most according to claim 7 is compound, its
It is characterised by, before the film described in step 3, regulation solution and the surface tension of substrate, reduce solution in suprabasil contact
Angle.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610703852.6A CN106297966A (en) | 2016-08-22 | 2016-08-22 | Nesa coating that a kind of metal nanometer line oxidation-resistant material is compound and preparation thereof |
| PCT/CN2017/098069 WO2018036428A1 (en) | 2016-08-22 | 2017-08-18 | Metal nanowire-oxidation-resistant material combined transparent conductive film and preparation therefor |
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|---|---|---|---|
| CN201610703852.6A CN106297966A (en) | 2016-08-22 | 2016-08-22 | Nesa coating that a kind of metal nanometer line oxidation-resistant material is compound and preparation thereof |
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| WO (1) | WO2018036428A1 (en) |
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