CN105802452B - A kind of graphene composite coating, graphene composite coating and preparation method thereof - Google Patents
A kind of graphene composite coating, graphene composite coating and preparation method thereof Download PDFInfo
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Abstract
The present invention provides a kind of graphene composite coatings, it is made of resin, graphene, oligomer of phenylamine, decentralized medium and coating additive, mass percent shared by the graphene described in graphene composite coating is 0.01%~5%, which is dispersed in the resin and forming pi-pi bond with oligomer of phenylamine.The present invention also provides a kind of preparation method of graphene composite coating and graphene composite coatings.
Description
Technical field
The present invention relates to a kind of anticorrosive paint and corrosion-inhibiting coating more particularly to a kind of compound paintings of graphene based on graphene
Layer, graphene composite coating and preparation method thereof.
Background technique
Anticorrosive paint, etch-proof paint can be played the role of to metal etc. by referring to.Country was always right in recent years
The ocean of the earth 7/10ths increases dynamics of investment, and anticorrosive paint has become the important fresh combatants of paint field, anticorrosive paint
Increasing effect is played, development prospect is considerable.Current common anticorrosive paint has epoxy coating, epoxy novolac
Coating, anti-corrosion polyurethane coating etc..This kind of coating generally uses high molecular polymer or resin, causes in film forming procedure, meeting
Micropore is left, corrosive media can gradually be permeated by micropore in the actual use process, and then corrosion metallic matrix.
Graphene as a kind of new carbon, because its with outstanding electronic conductivity energy, Wear-resistant performance and
High specific surface area and cause extensive research interest.However, graphene is directly added to high molecular polymer or tree
In rouge, graphene is easy to happen reunion due to π-πconjugation and Van der Waals force suction-operated, and is difficult to be dispersed in height
In Molecularly Imprinted Polymer or resin, micropore is caused to still remain, the protection effect of the coating of formation is poor.
Summary of the invention
In view of the deficiencies of the prior art, the main purpose of the present invention is to provide a kind of graphene composite coatings, graphene
Composite coating and preparation method thereof, graphene uniform is scattered in resin in the graphene composite coating, obtained coating
It is strong with good resistant to water penetration, protective capacities, it can be used as anticorrosive paint applied to relatively harsh corrosion such as ship, bridges
In environment.
The present invention provides a kind of graphene composite coating, by resin, graphene, oligomer of phenylamine, decentralized medium and painting
Expect auxiliary agent composition, mass percent shared by the graphene described in graphene composite coating is 0.01%~5%, the graphene
It is dispersed in the resin and forming pi-pi bond with oligomer of phenylamine.
Wherein, the mass ratio of the oligomer of phenylamine and graphene is 1:10~10:1.
Wherein, the diameter of the graphene is 5 μm~50 μm.
Wherein, the oligomer of phenylamine is aniline tripolymer, in Tetraaniline, aniline pentamer, six aggressiveness of aniline
A kind of or combination.
Wherein, the decentralized medium is one of toluene, dimethylbenzene, acetone, tetrahydrofuran, ethyl alcohol and dimethyl sulfoxide
Or combination.
Wherein, the resin is epoxy resin, acrylic resin, polyurethane resin, acrylated polyurethane resin and amino
One of resin or combination.
Wherein, the coating additive includes anti-settling agent, defoaming agent and levelling agent, the anti-settling agent be fumed silica,
One of polyamide wax and organobentonite or combination, the defoaming agent are dimethicone, ether ester compound, modified mineral
One of oil, polyoxyethanyl glycerin ether, small molecule metallorganic and silicon modified organic polymer or combination, the levelling agent
For butyl glycol ether, cellaburate, polyacrylate, silicone oil, hydroxymethyl cellulose, polydimethylsiloxane, polymethyl-benzene
One of radical siloxane and modified organic silicon compound or combination.
The present invention also provides a kind of preparation methods of graphene composite coating comprising following steps: by oligomer of phenylamine
With graphene dispersion in decentralized medium, make oligomer of phenylamine be uniformly mixed with graphene and oligomer of phenylamine and graphene it
Between formed pi-pi bond obtain graphene dispersing solution；One resin is provided, the graphene dispersing solution is added into the resin and is mixed
Uniformly, mixture A is obtained；Coating additive is added into the mixture A, obtains graphene composite coating, wherein in the stone
Mass percent shared by graphene described in black alkene composite coating is 0.01%~5%.
The present invention also provides a kind of graphene composite coatings, by resin, graphene, oligomer of phenylamine and coating additive group
Be 0.01%~5% at, mass percent shared by the graphene described in graphene composite coating, the graphene by with benzene
Amine oligomer forms pi-pi bond and is dispersed in the resin.
Wherein, mass percent shared by the resin described in graphene composite coating is 80%~95%, the aniline
Mass percent shared by oligomer is 0.01%~5%, and mass percent shared by the coating additive is 1%~10%.
Compared to the prior art, in graphene composite coating provided by the invention, benzene is passed through by the surface to graphene
The modifying and decorating of amine oligomer greatly improves the dispersibility and chemical stability of graphene, so that the graphene uniform point
It dissipates in the resin, and graphene has good hydrophobic performance, therefore in application process, hydrone can be effectively suppressed in shape
At graphene composite coating adsorption.Meanwhile graphene has two-dimensional slice structure, it is evenly dispersed in coating,
After forming graphene composite coating, graphene can be layering, and form fine and close isolation layer, thus small molecule corrosive medium
(hydrone, chloride ion etc.) is difficult to play the role of physical isolation outstanding by this layer of fine and close isolation layer.That is, obtained
Graphene composite coating have good resistant to water penetration, stronger protective capacities and excellent anti-corrosion effect.Also,
The problem of graphene composite coating is free of the heavy metal elements such as In, Sn, will not bring heavy metal pollution.It is provided by the invention
The preparation method of graphene composite coating, is innovated by preparation process, can be obtained with preferably dispersibility and chemical stability
Graphene composite coating, preparation process is simple, low in cost, is conducive to industrialization.
Detailed description of the invention
Fig. 1 is the synthesis process schematic diagram of aniline tripolymer of the present invention.
Fig. 2 is graphene dispersing solution (right side) and untreated graphene after toluene disperses (left side) described in embodiment 1
Photo.
Fig. 3 is the transmission electron microscope photo of graphene dispersing solution described in embodiment 1.
Fig. 4 a is surface topography photo of the pure polyurethane coating of comparative example 2 after salt mist experiment 500 hours.
Fig. 4 b is surface topography photo of the resulting graphene composite coating of embodiment 3 after salt mist experiment 500 hours.
Fig. 5 a is the resistance that 1 epoxy coating of comparative example impregnates the ac impedance spectroscopy in 8 days in 3.5wt%NaCl solution
Anti- complex plane figure.
Fig. 5 b is the wave that 1 epoxy coating of comparative example impregnates the ac impedance spectroscopy in 8 days in 3.5wt%NaCl solution
Spy's figure.
Fig. 5 c is that the resulting graphene composite coating of embodiment 2 impregnates the resistance of the exchange in 8 days in 3.5wt%NaCl solution
The impedance complex plane figure of anti-spectrum.
Fig. 5 d is that the resulting graphene composite coating of embodiment 2 impregnates the resistance of the exchange in 8 days in 3.5wt%NaCl solution
The Bode diagram of anti-spectrum.
Fig. 6 is that the resulting graphene composite coating of embodiment 2 (corresponding solid line) is (corresponding with 1 epoxy coating of comparative example
Dotted line) impregnated 8 days in 3.5wt%NaCl solution after polarization curve.
Fig. 7 is that the resulting graphene composite coating of embodiment 2 (corresponding b curve) is (corresponding with 1 epoxy coating of comparative example
A curve) lgQ in 8 days is impregnated in 3.5wt%NaCl solutionc-t1/2Curve and equation of linear regression (wherein, QcFor coating
Capacitor, t are the testing time).
Fig. 8 is 2 resulting graphene composite coating (c curve) of embodiment, (corresponding b is bent for 1 epoxy coating of comparative example
Line) impregnated 8 days in 3.5wt%NaCl solution with Commercial epoxy zinc-rich coating (corresponding a curve) after AC impedance spectroscopy.
Specific embodiment
Below with reference to attached drawing to graphene composite coating provided by the invention, graphene composite coating and preparation method thereof
It is described further.
The embodiment of the present invention provides a kind of preparation method of graphene composite coating.This method comprises the following steps:
Process (1): by oligomer of phenylamine and graphene dispersion in decentralized medium, mix oligomer of phenylamine with graphene
It uniformly and between oligomer of phenylamine and graphene forms pi-pi bond and obtains graphene dispersing solution.The oligomer of phenylamine has good
Good dissolubility, dissolves in the decentralized medium.The oligomer of phenylamine is for graphene described in modification.Specifically,
Due in the oligomer of phenylamine phenyl ring and graphene-structured it is close, thus the oligomer of phenylamine can between graphene shape
It realizes at pi-pi bond and is mixed with graphene uniform.It should be pointed out that using π-π is formed between oligomer of phenylamine and graphene
Key, this mode are different from grafting modification, the structure of graphene itself are not destroyed, also different from physical cladding stone
The macromolecule of black alkene does not sacrifice the performance of graphene.That is, by oligomer of phenylamine modification graphene,
Only make dispersibility and the stability of graphene more preferable, and do not destroy the structure of graphene, does not also reduce the original property of graphene
Energy.
It is appreciated that graphene uniform can be made to disperse by the dispersing method of high-speed stirred, ultrasound, ball milling and/or sand milling,
Further it is uniformly mixed graphene with oligomer of phenylamine.
The structure of the graphene is unlimited comprising graphene nanometer sheet, graphene nanobelt, lacks graphene micron film
Layer graphene (2-5 layers), multi-layer graphene (2-9 layers), graphene quantum dot and these graphite alkenes materials derivative).
The definition of the grapheme material can be found in document " All in the graphene family-A recommended
nomenclature for two-dimensional carbon materials".The grapheme material is also selected from thickness
Degree≤20nm, it is highly preferred that thickness≤10nm material.In the present embodiment, the grapheme material thickness preferably≤3nm,
Grapheme material is thinner, and flexibility is better, is more easily worked.The preparation method of the grapheme material is unlimited, using ability
Graphene product known to field technique personnel is prepared with conventional preparation method.Grapheme material of the invention is preferably peaceful
The graphene product that Bo Moxi Science and Technology Ltd. provides.Grapheme material can selected from chemical oxidization method such as Brodie method,
The graphene oxide of any one method preparation in Hummers method or Staudenmaier method is thermally expanded graphene obtained
Material.The grapheme material of mechanical stripping, liquid phase removing or electrochemical stripping preparation can also be selected.The diameter of the graphene
It is 5 μm~50 μm.The oligomer of phenylamine is aniline tripolymer, Tetraaniline, aniline pentamer, one in six aggressiveness of aniline
Kind or combination.The structural formula of the aniline tripolymer please refers to Fig. 1.The decentralized medium is toluene, dimethylbenzene, acetone, tetrahydro
One or more of furans, ethyl alcohol and dimethyl sulfoxide mixed solvent.The mass ratio of the oligomer of phenylamine and graphene is
1:10~10:1.Preferably, the mass ratio of the oligomer of phenylamine and graphene is 2:1~1:1.
Process (2): a resin is provided, the graphene dispersing solution is added into the resin and is uniformly mixed, is mixed
Close object A.Graphene dispersing solution can be made to be dispersed in resin by the dispersing method of high-speed stirred, ultrasound, ball milling and/or sand milling
In, further it is scattered in graphene uniform in resin.The resin is epoxy resin, acrylic resin, polyurethane resin, third
One of olefin(e) acid polyurethane resin and amino resins or combination.
Process (3): coating additive is added into the mixture A, obtains graphene composite coating.The coating additive packet
Include anti-settling agent, defoaming agent and levelling agent.The anti-settling agent is one of fumed silica, polyamide wax and organobentonite
Or combination.The defoaming agent is dimethicone, ether ester compound, modified mineral oil, polyoxyethanyl glycerin ether, small molecule metal
One of organic matter and silicon modified organic polymer or combination.The levelling agent is butyl glycol ether, cellaburate, poly- third
In olefin(e) acid esters, silicone oil, hydroxymethyl cellulose, polydimethylsiloxane, polymethylphenylsiloxane and modified organic silicon compound
One kind or combination.It is appreciated that the graphene composite coating may also include curing agent.The curing agent can be polyamide,
For accelerating the graphene composite coating solidification process.
Mass percent shared by graphene described in obtained graphene composite coating is 0.01%~5%, preferably,
0.2%~0.5%.
The present invention also provides a kind of graphene composite coatings prepared using the above method.The graphene composite coating is by setting
Rouge, graphene, oligomer of phenylamine, decentralized medium and coating additive composition.Shared by the graphene described in graphene composite coating
Mass percent be 0.01%~5%.The graphene is dispersed in the tree and forming pi-pi bond with oligomer of phenylamine
In rouge.
The present invention also provides a kind of obtained graphene composite coatings prepared using above-mentioned graphene composite coating.Specifically
, above-mentioned graphene composite coating is coated on matrix by means such as blade coating, roller coating, in the graphene composite coating
Decentralized medium volatilization after form graphene composite coating.The graphene composite coating is oligomeric by resin, graphene, aniline
Object and coating additive composition.Mass percent shared by the graphene described in graphene composite coating is 0.01%~5%.It should
Graphene is dispersed in the resin and forming pi-pi bond with oligomer of phenylamine.Described in graphene composite coating
Mass percent shared by resin is 80%~95%, and mass percent shared by the oligomer of phenylamine is 0.01%~5%,
Mass percent shared by the coating additive is 1%~10%.
In graphene composite coating provided by the invention, repaired by the surface to graphene by the modification of oligomer of phenylamine
Decorations, greatly improve the dispersibility and chemical stability of graphene, so that the graphene uniform is scattered in the resin, and
Graphene has good hydrophobic performance, therefore in application process, hydrone can be effectively suppressed in the compound painting of graphene of formation
The adsorption of layer.Meanwhile graphene has two-dimensional slice structure, evenly dispersed in coating, when being formed, graphene is compound
After coating, graphene can be layering, and form fine and close isolation layer, thus small molecule corrosive medium (hydrone, chloride ion etc.)
It is difficult to play the role of physical isolation outstanding by this layer of fine and close isolation layer.That is, obtained graphene composite coating has
There are good resistant to water penetration, stronger protective capacities and excellent anti-corrosion effect.Also, the graphene composite coating
Without heavy metal elements such as In, Sn, the problem of heavy metal pollution will not be brought.The system of graphene composite coating provided by the invention
Preparation Method is innovated by preparation process, can obtain the graphene composite coating with preferably dispersibility and chemical stability, preparation
Simple process and low cost is conducive to industrialization.
To further describe the present invention, here is the preparation method of the graphene composite coating, graphene composite coating,
Specific embodiment under different parameters:
Embodiment 1:
By 1.0g aniline tripolymer (synthesis process is shown in Fig. 1) and 1.0g graphene (purchased from the limited public affairs of Ningbo Mo Xi science and technology
Department) it is dispersed in 1.0L toluene solution, ultrasonic disperse 1 hour, obtain graphene dispersing solution.Graphene is modified through aniline tripolymer
The content in toluene reaches 1g/L afterwards.The graphene dispersing solution and comparison of the untreated graphene after toluene disperses
Effect is shown in Fig. 2.The electronic transmission electromicroscopic photograph of the graphene dispersing solution is shown in Fig. 3.By Fig. 2 and Fig. 3 as it can be seen that graphene passes through benzene
It can be dispersed in toluene after the modification of amine tripolymer, graphene structure in the form of sheets in the graphene dispersing solution.
The graphene dispersing solution is added in 45g epoxy resin (model E44, purchased from Jiangsu Wujiang resultant force resin
Factory), mixture A is obtained after mixing.Sequentially added again into the mixture A 2g levelling agent, 4g defoaming agent, 2g anti-settling agent and
45g polyamide curing agent stirs evenly to get graphene composite coating is arrived.
Embodiment 2:
By 2.0g Tetraaniline and 1.0g graphene dispersion in 1.0L toluene solution, ultrasonic disperse 1 hour, obtain
Graphene dispersing solution.Content of the graphene after Tetraaniline is modified in toluene reaches 1g/L.
The graphene dispersing solution is added in 46g epoxy resin ((model E44, purchased from Jiangsu Wujiang resultant force resin
Factory), mixture A is obtained after mixing.Sequentially added again into the mixture A 1g levelling agent, 1g defoaming agent, 1g anti-settling agent and
46g polyamide curing agent stirs evenly to get graphene composite coating is arrived.
Obtained graphene composite coating is coated on a plain steel, after toluene volatilization, it is compound to obtain graphene
Coating.
For comparative experiments effect, it is also prepared for 1 epoxy coating of comparative example.Epoxy resin described in comparative example 1 applies
The preparation method of layer with embodiment 2, unlike, graphene dispersing solution is not added.
The survey of antiseptic property is carried out to graphene composite coating described in embodiment 2 and the epoxy coating of comparative example 1
Examination.Specifically, by the graphene composite coating and the epoxy coating of comparative example 1 respectively in 3.5wt%NaCl solution
It impregnates 8 days, then uses Shanghai morning China CHI660E electrochemical workstation, respectively obtain graphene composite coating and epoxy resin
The ac impedance spectroscopy (see Fig. 5 a to Fig. 5 d) and dynamic potential polarization curve of coating (see Fig. 6).By Fig. 5 a to Fig. 5 d, Fig. 6 it is found that institute
It is bigger than the impedance of epoxy coating to state graphene composite coating.After impregnating 8 days, the corrosion current of graphene composite coating
Density is 5.23nAcm-2, and the corrosion current density of epoxy coating is 158nAcm-2.This explanation passes through aniline
The graphene alkene of the modifying and decorating of oligomer can be dispersed in resin, to substantially increase the anti-of graphene composite coating
Rotten performance.
Resistant to water penetration performance is carried out to graphene composite coating described in embodiment 2 and the epoxy coating of comparative example 1
Test.Specifically, by being fitted to AC impedance, with lgQc(Qc is coating capacitor) is to t1/2Mapping, obtains Fig. 7.
By linear fit, the equation of linear regression of epoxy coating and graphene composite coating can be respectively obtained, and then is calculated
The diffusion coefficient for obtaining epoxy coating and graphene composite coating is respectively 6.35 × 10-11m2/ d and 9.1 × 10-12m2/d。
This explanation can be dispersed in resin by the graphene of the modifying and decorating of oligomer of phenylamine, to slow down hydrone in stone
Diffusion velocity in black alkene composite coating.
By graphite ene coatings and pure epoxy coating, Commercial epoxy zinc-rich coating passes through comparison in 3.5wt%NaCl solution
AC impedance spectroscopy after 8 days (see Fig. 8), it is seen that the anti-corrosion effect of graphene epoxy coating is best.
Embodiment 3:
By 1.5g aniline tripolymer and 1.5g graphene dispersion in 1.0L toluene solution, obtain within ultrasonic disperse 1 hour
Graphene dispersing solution.Content of the graphene after the modification of aniline tripolymer in toluene reaches 1.5g/L.
The graphene dispersing solution is added in 90g polyurethane the mixing (purchased from Ningbo Flywheel Paint Co., Ltd.)
After obtain mixture A.2g levelling agent, 3g defoaming agent, 2g anti-settling agent are sequentially added into the mixture A again, is stirred evenly, i.e.,
Obtain graphene composite coating.
Obtained graphene composite coating is coated on a plain steel, after toluene volatilization, it is compound to obtain graphene
Coating.
For comparative experiments effect, it is also prepared for the pure polyurethane coating of comparative example 2.Pure polyurethane described in comparative example 2 applies
The preparation method of layer with embodiment 3, unlike, graphene dispersing solution is not added.
Salt spray resistance is carried out to the pure polyurethane coating of graphene composite coating described in embodiment 3 and comparative example 2
Test.Specifically, the graphene composite coating and the pure polyurethane coating of comparative example 2 are respectively placed in salt spray test chamber,
It takes out, and is taken pictures after being dried at room temperature for (see Fig. 4 a and Fig. 4 b) after 1000 hours.By Fig. 4 a and Fig. 4 b as it can be seen that pure poly- ammonia
The surface of ester coating has apparent etch pit to occur, and the surface of graphene composite coating does not have apparent corrosion phenomenon.
Embodiment 4:
By 1.5g aniline tripolymer and 2g graphene dispersion in 1.0L toluene solution, ultrasonic disperse 1 hour, stone is obtained
Black alkene dispersion liquid.Content of the graphene after Tetraaniline is modified in toluene reaches 2g/L.
The graphene dispersing solution is added in 90g acrylic resin (purchased from the limited public affairs of Shandong Weifang Fuller new material
Department), mixture A is obtained after mixing.2g levelling agent, 2.5g defoaming agent, 2g anti-settling agent are sequentially added into the mixture A again,
It stirs evenly to get graphene composite coating is arrived.
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvements and modifications also fall within the scope of protection of the claims of the present invention.To these embodiments
A variety of modifications are it will be apparent that the general principles defined herein can be not for those skilled in the art
It is realized in other embodiments in the case where being detached from the spirit or scope of the present invention.Therefore, the present invention is not intended to be limited to this
These embodiments shown in text, and it is to fit to the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. a kind of graphene composite coating, which is characterized in that it is by resin, graphene, oligomer of phenylamine, decentralized medium and coating
Auxiliary agent forms, and mass percent shared by the graphene described in graphene composite coating is 0.01%~5%, and the graphene is logical
It crosses and forms pi-pi bond with oligomer of phenylamine and be dispersed in the resin；
The graphene composite coating is made by following steps:
By oligomer of phenylamine and graphene dispersion in decentralized medium, it is uniformly mixed oligomer of phenylamine with graphene and in aniline
Pi-pi bond is formed between oligomer and graphene obtains graphene dispersing solution；
One resin is provided, the graphene dispersing solution is added into the resin and is uniformly mixed, mixture A is obtained；
Coating additive is added into the mixture A, obtains graphene composite coating.
2. graphene composite coating according to claim 1, which is characterized in that the quality of the oligomer of phenylamine and graphene
Than for 1:10~10:1.
3. graphene composite coating according to claim 1, which is characterized in that the diameter of the graphene is 5 μm~50 μm.
4. graphene composite coating according to claim 1, which is characterized in that the oligomer of phenylamine be aniline tripolymer,
One of Tetraaniline, aniline pentamer, six aggressiveness of aniline or combination.
5. graphene composite coating according to claim 1, which is characterized in that the decentralized medium is toluene, dimethylbenzene, third
One of ketone, tetrahydrofuran, ethyl alcohol and dimethyl sulfoxide or combination.
6. graphene composite coating according to claim 1, which is characterized in that the resin is epoxy resin, acrylic acid tree
One of rouge, polyurethane resin, acrylated polyurethane resin and amino resins or combination.
7. graphene composite coating according to claim 1, which is characterized in that the coating additive includes anti-settling agent, defoaming
Agent and levelling agent, the anti-settling agent is one of fumed silica, polyamide wax and organobentonite or combines, described to disappear
Infusion is dimethicone, ether ester compound, modified mineral oil, polyoxyethanyl glycerin ether, small molecule metallorganic and modification
One of organosilicon polymer or combination, the levelling agent are butyl glycol ether, cellaburate, polyacrylate, silicon
One of oil, hydroxymethyl cellulose, polydimethylsiloxane, polymethylphenylsiloxane and modified organic silicon compound or group
It closes.
8. a kind of graphene composite coating, which is characterized in that it is made of resin, graphene, oligomer of phenylamine and coating additive,
Mass percent shared by the graphene described in graphene composite coating be 0.01%~5%, the graphene by with aniline
Oligomer forms pi-pi bond and is dispersed in the resin.
9. graphene composite coating according to claim 8, which is characterized in that the institute of the resin described in graphene composite coating
The mass percent accounted for is 80%~95%, and mass percent shared by the oligomer of phenylamine is 0.01%~5%, the painting
Expect that mass percent shared by auxiliary agent is 1%~10%.
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| CN201410844601.0A CN105802452B (en) | 2014-12-30 | 2014-12-30 | A kind of graphene composite coating, graphene composite coating and preparation method thereof |
| PCT/CN2015/095742 WO2016086796A1 (en) | 2014-12-02 | 2015-11-27 | Graphene dispersant and application thereof |
| EP15865917.7A EP3228592A4 (en) | 2014-12-02 | 2015-11-27 | DISPERSANT OF GRAPHENE AND ITS APPLICATION |
| TW104139658A TWI602611B (en) | 2014-12-02 | 2015-11-27 | Graphene dispersant and its application |
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| US10822501B2 (en) * | 2016-11-17 | 2020-11-03 | Ningbo Institute Of Materials Technology & Engineering, Chinese Academy Of Sciences | Hexagonal boron nitride epoxy compound anticorrosive paint, and preparation method and use thereof |
| CN106543728A (en) * | 2016-11-25 | 2017-03-29 | 德阳中碳新材料科技有限公司 | A kind of Graphene organic silicon rubber composite and preparation method thereof |
| GB2570733B (en) | 2018-02-06 | 2022-11-02 | Applied Graphene Mat Uk Ltd | Corrosion protection for metallic substrates |
| CN108641514A (en) * | 2018-05-28 | 2018-10-12 | 安徽开林新材料股份有限公司 | A kind of graphene antistatic coating and preparation method thereof |
| CN109160508B (en) * | 2018-09-14 | 2020-12-01 | 山东玉皇新能源科技有限公司 | Graphene slurry and preparation method thereof |
| CN109797452B (en) * | 2019-01-30 | 2021-04-13 | 华峰化学股份有限公司 | Method for modifying spandex by virtue of graphene with uniform micro-dispersion |
| CN110040712A (en) * | 2019-03-25 | 2019-07-23 | 天津大学 | The classifying porous hollow carbon sphere material of N doping and preparation method for supercapacitor |
| CN110093088B (en) * | 2019-04-24 | 2022-08-30 | 中国海洋大学 | Graphene-like self-dispersing coating and preparation method thereof |
| CN113512345A (en) * | 2020-04-09 | 2021-10-19 | 宣城亨旺新材料有限公司 | Waterproof heat-dissipating coating material and method for forming waterproof heat-dissipating structure using same |
| CN112724810B (en) * | 2020-09-21 | 2022-11-08 | 安徽三寸光反光材料有限公司 | High-weather-resistance reflective coating and preparation method thereof |
| CN113416452B (en) * | 2021-06-22 | 2022-03-18 | 广东鑫皇冠新材料有限公司 | Heat-conducting and heat-dissipating water-soluble fluoride coating and preparation method thereof |
| CN113881292B (en) * | 2021-11-09 | 2022-07-29 | 东莞泰仓合成材料有限公司 | Anti-permeability anticorrosive paint with good stability and strong adhesiveness and preparation method thereof |
| TW202348441A (en) * | 2022-06-02 | 2023-12-16 | 中原大學 | Process for preparing substrate structure |
| CN117925065B (en) * | 2022-10-26 | 2026-02-17 | 宝山钢铁股份有限公司 | Corrosion-resistant and wear-resistant polyurethane-silicone oil composite coating on carbon steel surface and preparation method thereof |
| CN116656198A (en) * | 2023-07-06 | 2023-08-29 | 深圳前海石墨烯产业有限公司 | A kind of graphene heat dissipation paint suitable for CPU radiator and preparation method thereof |
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| CN102702515A (en) * | 2012-05-28 | 2012-10-03 | 哈尔滨工程大学 | Graphene and polyaniline nanocomposite capable of absorbing high frequency electromagnetic wave as well as preparation method and application thereof |
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