CN107384112B - A kind of graphene-based anticorrosion coating material and preparation method thereof with the rust construction of water band - Google Patents
A kind of graphene-based anticorrosion coating material and preparation method thereof with the rust construction of water band Download PDFInfo
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- CN107384112B CN107384112B CN201710617182.0A CN201710617182A CN107384112B CN 107384112 B CN107384112 B CN 107384112B CN 201710617182 A CN201710617182 A CN 201710617182A CN 107384112 B CN107384112 B CN 107384112B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 114
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 108
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000011248 coating agent Substances 0.000 title claims abstract description 43
- 238000000576 coating method Methods 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- 238000010276 construction Methods 0.000 title claims abstract description 35
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000000463 material Substances 0.000 title claims abstract description 34
- 239000002105 nanoparticle Substances 0.000 claims abstract description 62
- 239000002131 composite material Substances 0.000 claims abstract description 42
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 claims abstract description 26
- -1 organic siliconresin Substances 0.000 claims abstract description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 14
- 239000010703 silicon Substances 0.000 claims abstract description 14
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 13
- 239000013522 chelant Substances 0.000 claims abstract description 13
- 239000013530 defoamer Substances 0.000 claims abstract description 13
- 229910003460 diamond Inorganic materials 0.000 claims abstract description 13
- 239000010432 diamond Substances 0.000 claims abstract description 13
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000428 dust Substances 0.000 claims abstract description 13
- 239000003822 epoxy resin Substances 0.000 claims abstract description 13
- 239000010452 phosphate Substances 0.000 claims abstract description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 13
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 13
- 244000226021 Anacardium occidentale Species 0.000 claims abstract description 8
- 235000020226 cashew nut Nutrition 0.000 claims abstract description 8
- 239000010466 nut oil Substances 0.000 claims abstract description 8
- 229920001721 polyimide Polymers 0.000 claims abstract description 8
- 239000009719 polyimide resin Substances 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 229920002050 silicone resin Polymers 0.000 claims abstract description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 51
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 24
- 238000004108 freeze drying Methods 0.000 claims description 21
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 16
- 239000006185 dispersion Substances 0.000 claims description 14
- 235000019441 ethanol Nutrition 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 229960004756 ethanol Drugs 0.000 claims description 11
- 229910052738 indium Inorganic materials 0.000 claims description 9
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 8
- 239000003921 oil Substances 0.000 claims description 8
- 235000019198 oils Nutrition 0.000 claims description 8
- 229910000077 silane Inorganic materials 0.000 claims description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 7
- 239000004593 Epoxy Substances 0.000 claims description 7
- 229910002804 graphite Inorganic materials 0.000 claims description 7
- 239000010439 graphite Substances 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 239000007822 coupling agent Substances 0.000 claims description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 5
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- 230000008878 coupling Effects 0.000 claims description 5
- 238000010168 coupling process Methods 0.000 claims description 5
- 238000005859 coupling reaction Methods 0.000 claims description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 4
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 4
- 238000002242 deionisation method Methods 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 2
- LMQORFSQFKHATF-UHFFFAOYSA-N dimethoxy-methyl-[4-(oxiran-2-yl)butyl]silane Chemical compound CO[Si](C)(OC)CCCCC1CO1 LMQORFSQFKHATF-UHFFFAOYSA-N 0.000 claims description 2
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 claims description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011238 particulate composite Substances 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims 1
- 238000007710 freezing Methods 0.000 claims 1
- 230000008014 freezing Effects 0.000 claims 1
- INJVFBCDVXYHGQ-UHFFFAOYSA-N n'-(3-triethoxysilylpropyl)ethane-1,2-diamine Chemical compound CCO[Si](OCC)(OCC)CCCNCCN INJVFBCDVXYHGQ-UHFFFAOYSA-N 0.000 claims 1
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical group CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims 1
- 239000004408 titanium dioxide Substances 0.000 claims 1
- 229910000831 Steel Inorganic materials 0.000 abstract description 3
- 230000002421 anti-septic effect Effects 0.000 abstract description 3
- 239000010959 steel Substances 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 25
- 238000007306 functionalization reaction Methods 0.000 description 7
- 150000001336 alkenes Chemical class 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 2
- 230000001476 alcoholic effect Effects 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- MYPJGWRJVADZCJ-UHFFFAOYSA-N C(C1CO1)CCCC(OOOC)C Chemical compound C(C1CO1)CCCC(OOOC)C MYPJGWRJVADZCJ-UHFFFAOYSA-N 0.000 description 1
- 238000006424 Flood reaction Methods 0.000 description 1
- 239000006087 Silane Coupling Agent Substances 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 229920013822 aminosilicone Polymers 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- GPLRAVKSCUXZTP-UHFFFAOYSA-N diglycerol Chemical compound OCC(O)COCC(O)CO GPLRAVKSCUXZTP-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 210000000232 gallbladder Anatomy 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- PHQOGHDTIVQXHL-UHFFFAOYSA-N n'-(3-trimethoxysilylpropyl)ethane-1,2-diamine Chemical compound CO[Si](OC)(OC)CCCNCCN PHQOGHDTIVQXHL-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011150 reinforced concrete Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- QQQSFSZALRVCSZ-UHFFFAOYSA-N triethoxysilane Chemical compound CCO[SiH](OCC)OCC QQQSFSZALRVCSZ-UHFFFAOYSA-N 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/04—Condensation polymers of aldehydes or ketones with phenols only
- C09D161/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C09D161/14—Modified phenol-aldehyde condensates
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3045—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Paints Or Removers (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
The invention discloses a kind of graphene-based anticorrosion coating materials and preparation method thereof with the rust construction of water band, including component A and component B, the component A is made of following raw material: epoxy resin, organic siliconresin, nanoparticle/graphene composite material, aqueous phosphate chelate, barium sulfate, talcum powder, diamond dust, the silicone resin, organic silicon defoamer of Ultra-low molecular weight；The component B is made of following raw material: cashew nut oil modified phenolic aldehyde polyimide resin.Preparation method are as follows: stir evenly all components of component A and component B respectively；Component A obtained and component B are uniformly mixed according to weight ratio 7-10:1 to get the product.The invention has the characteristics that providing a kind of energy band water, anticorrosion coating material with steel construction in rust, band dirty coating ocean and preparation method thereof, and antiseptic property is increased using nanoparticle/graphene composite material in coating material.
Description
Technical field
The present invention relates to anticorrosion coating materials, and in particular to a kind of graphene-based anticorrosion coating material with the rust construction of water band
And preparation method thereof.
Background technique
According to statistics, in the world every year due to corrosion caused by loss account for the 2%-4% of national economy total output value, than because of fire
Loss summation caused by the natural calamities such as calamity, disaster caused by a windstorm, floods and earthquake is also big, therefore each coastal state in the world is highly heavy
It works depending on marine corrosion and Protective Research.China is ocean big country, possesses more than 18000 kilometers of coastline, at present in marine oil
The fields such as gas field development, port construction, bridge spanning the sea, seabed tunnel, Marine engineering and deep-sea exploration are built and a large amount of building
Various steel constructions and reinforced concrete structure facility, once disastrous corrosion occurs, it will lead to seriously destruction and tremendous economic
Loss.
Graphene itself has the performances such as excellent electricity, mechanics and calorifics, and the lamellar structure of itself is with superpower
Shielding, corrosive medium can be stopped to enter coating, applied it in anticorrosive paint, can both improve the performance of coating, such as
Flexibility, hardness, shock resistance etc., and its corrosion resistance can be enhanced.But the high chemical stability of graphene itself and dredge
It is aqueous, so that it is difficult dispersion and functionalization.And graphene oxide (GO) be one kind on surface and edge by hydroxyl, carboxyl and
The substance of the unimolecule carbon-coating of the oxygen-containing functional groups such as epoxy group composition, sufficient oxygen-containing group not only make GO and organic polymer very
Good compatibility, and it is made to be easier to functionalization.However, due in GO Van der Waals force interaction, show solid matter heap
Stack structure causes to be unevenly distributed and be difficult to the problem of removing in the epoxy.Therefore, grapheme modified with inorganic nano material
Nano particle can be loaded to the surface GO using its steric hindrance by thin slice, prevent the reunion between graphene oxide layer, make it easily
In being distributed in large arch dam system.
Summary of the invention
For needing to clear up in the iron rust of construction surface, dirt before the construction of existing coating material, can just construct, and
Coating will coat 2 times, and coating layer thickness just can make coating salt-fog resistant time reach 4000h in 1.6mm or more.The present invention provides one kind
Energy band water, with rust, the graphene-based anticorrosion coating material of band dirt coating steel construction and preparation method thereof.The coating material construction party
Just, long service life, while mitigating coating layer thickness, save raw material, significantly increase antiseptic property.
A kind of graphene-based anticorrosion coating material with the rust construction of water band, including component A and component B, the first group
Part is prepared by each component of following weight parts:
5-10 parts of 45-55 parts of epoxy resin, the organic siliconresin of Ultra-low molecular weight, nanoparticle/graphene composite material
0.5-2 parts, 5-10 parts of aqueous phosphate chelate, 5-10 parts of barium sulfate, 5-10 parts of talcum powder, 5-10 parts of diamond dust, siloxanes
1-1.5 parts of resin, 0.1-0.5 parts of organic silicon defoamer；
The component B are as follows: 100 parts of cashew nut oil modified phenolic aldehyde polyimide resin.
The graphene-based anticorrosion coating material with the rust construction of water band, preparation method include the following steps:
(1) according to the parts by weight of each component of component A, each substance is weighed, the high-power height of all components in component A
Under conditions of 1500-2500 revs/min, dispersion is packed and stored fast dispersion machine after 1-2 hours；
It (2) is that 7-10:1 uniformly mixes to get the product according to weight ratio by component A obtained and component B.
The preparation method of the nanoparticle/graphene composite material, comprising the following steps:
(1) using natural flake graphite as raw material, graphene oxide is prepared using Hummers method is improved；
(2) nano particle is distributed in the ethanol solution containing amino silicane coupling agent that volume fraction is 2%, ultrasound
Deionized water is added dropwise at 90 DEG C of water-bath by 2h, reacts 10h, and obtained product dehydrated alcohol and deionized water are washed three times respectively,
Functionalized nano particle is obtained after freeze-drying；
(3) graphene oxide prepared by step (1) is distributed to volume fraction is 2% containing epoxy silane coupling
In ethanol solution, deionized water is added dropwise at 90 DEG C of water-bath by ultrasonic 2h, reacts 10h, obtained product dehydrated alcohol and deionization
Water washs three times respectively, and functional graphene oxide is obtained after freeze-drying；
(4) functional graphene oxide made from step (3) is added in n,N-Dimethylformamide, ultrasonic 2h adds
Enter the functionalized nano particle of step (2) preparation, ultrasonic 2h reacts 12h at 90 DEG C of oil bath, obtains mixed solution；
(5) reducing agent solution is instilled in mixed solution, obtained product dehydrated alcohol and deionized water are washed respectively
Three times, graphene/nanometer particulate composite is obtained after freeze-drying.
In the preparation method of nanoparticle/graphene composite material, selected described in step (2) containing amino silicane coupling agent
With 3- TSL 8330, gamma-aminopropyl-triethoxy-silane, N- aminoethyl-gamma-aminopropyl-triethoxy silicon
Alkane, N- (β-aminoethyl)-γ-aminopropyltrimethoxysilane, N- β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane
One of.
In the preparation method of nanoparticle/graphene composite material, nano particle described in step (2) selects nano oxygen
Change zirconium (ZrO2), nano silica (SiO2), nano-titanium dioxide (TiO2), nano aluminium oxide (Al2O3One of).
In the preparation method of nanoparticle/graphene composite material, nano particle described in step (2) and contain amino silicone
The amount ratio of alkane coupling agent is 1-5g:100mL.
In the preparation method of nanoparticle/graphene composite material, nano particle described in step (2) is gone with what is be added dropwise
The amount ratio of ionized water is 1-2g:200mL.
In the preparation method of nanoparticle/graphene composite material, epoxy silane coupling is contained described in step (3)
γ-glycidyl ether oxygen propyl trimethoxy silicane, γ-glycidylpropyl methyl dimethoxysilane, 3- is selected to shrink
One of glyceryl ether oxypropyl triethoxysilane, 2- (3,4- 7-oxa-bicyclo[4.1.0 base) ethyl trimethoxy silane.
In the preparation method of nanoparticle/graphene composite material, graphene oxide described in step (3) and contain epoxy
The amount ratio of base silane coupling agent is 1-5g:100mL；Graphene oxide described in step (3) and the deionized water of dropwise addition
Amount ratio is 1-2g:200mL.
In the preparation method of nanoparticle/graphene composite material, functional graphene oxide described in step (4) and
The mass volume ratio of N,N-dimethylformamide is 1-2g:200mL；Functional graphene oxide and function described in step (4)
The weight ratio that nano particle can be changed is 2-3:1；One in the selection of reducing solution described in step (5) hydrazine hydrate, sodium borohydride
Kind；The volume ratio of mixed solution described in step (5) and reducing solution is 3-5:1.
The advantages of graphene-based anticorrosion coating material and preparation method thereof that the present invention constructs with water band rust, is:
1. the graphene-based anticorrosion coating material and preparation method thereof with the rust construction of water band, has selected nano particle/graphite
Alkene composite material, can be evenly dispersed in the coating, forms relatively complete sheet shielding construction, enhances coating antiseptic
Can, reduce best coating layer thickness, raw material and construction cost can be saved.
2. the graphene-based anticorrosion coating material and preparation method thereof with the rust construction of water band, coating material have very strong infiltration
Effect thoroughly, may penetrate among rust and iron plate, rust is wrapped, and prevent corrosion from continuing to occur, while inorganic filler energy and water
Reaction, so band water, application over rust can be realized.
Detailed description of the invention
Fig. 1 is the SEM photograph of nanoparticle/graphene composite material；
Specific embodiment:
Embodiment one
A kind of graphene-based anticorrosion coating material with the rust construction of water band, including component A and component B.Its main component
By weight:
The component A each component are as follows: 10 parts of 50 parts of epoxy resin, the organic siliconresin of Ultra-low molecular weight, nano particle/
1.5 parts of graphene composite material, 7 parts of aqueous phosphate chelate, 10 parts of barium sulfate, 10 parts of talcum powder, 10 parts of diamond dust, silicon oxygen
1.2 parts of alkane resin, 0.3 part of organic silicon defoamer；
The component B each component are as follows: 100 parts of cashew nut oil modified phenolic aldehyde polyimide resin.
Prepare the preparation method of the graphene-based anticorrosion coating material with the rust construction of water band of the present embodiment, including following step
It is rapid:
(1) 50 parts of the epoxy resin of the Ultra-low molecular weight in component A, 10 parts of organic siliconresin, nano particle/graphite
1.5 parts of alkene composite material, 7 parts of aqueous phosphate chelate, 10 parts of barium sulfate, 10 parts of talcum powder, 10 parts of diamond dust, siloxanes tree
1.2 parts of rouge, 0.3 part of organic silicon defoamer, with Large-power High-Speed dispersion machine under conditions of 1500 revs/min, after dispersion 2 hours
It is packed and stored；
It (2) is that 10:1 uniformly mixes to get the product according to weight ratio by component A obtained and second group.
In the present embodiment, nanoparticle/graphene composite material the preparation method is as follows:
(1) preparation method of graphene oxide is the same as the step (1) in example IV；
(2) 40mg nano-titanium oxide is distributed to the 3- TSL 8330 that 50mL volume fraction is 2%
In ethanol solution, 6mL deionized water is added dropwise at 90 DEG C of water-bath by ultrasonic 2h, reacts 10h, obtained product dehydrated alcohol and goes
Ionized water washs three times respectively, and functionalization titanium oxide is obtained after freeze-drying；
(3) 40mg graphene oxide is distributed to 50mL volume fraction is 2% γ-glycidyl ether oxygen propyl trimethoxy
In the alcohol solvent of silane, ultrasonic 2h reacts 10h at 90 DEG C of water-bath, obtained product dehydrated alcohol and deionized water difference
Washing three times, obtains functional graphene oxide after freeze-drying；
(4) 40mg functional graphene oxide is added to 6.5mLN, in dinethylformamide, function is added in ultrasonic 2h
Nano particle can be changed, ultrasonic 2h reacts 12h at 90 DEG C of oil bath, obtains mixed solution；
(5) in mixed solution instill 2.0mL 80wt% hydrazine hydrate solution, obtained product dehydrated alcohol and go from
Sub- water washs respectively, and nanoparticle/graphene composite material is obtained after freeze-drying.
The performance test results of the present embodiment are as follows:
Embodiment two
A kind of graphene-based anticorrosion coating material with the rust construction of water band, including component A and component B.Its main component
By weight:
The component A each component are as follows: 9 parts of 53 parts of epoxy resin, organic siliconresin, the nano particle/stone of Ultra-low molecular weight
1 part of black alkene composite material, 8.8 parts of aqueous phosphate chelate, 9 parts of barium sulfate, 9 parts of talcum powder, 9 parts of diamond dust, siloxanes tree
1 part of rouge, 0.2 part of organic silicon defoamer；
The component B each component are as follows: 100 parts of cashew nut oil modified phenolic aldehyde polyimide resin.
Prepare the preparation method of the graphene-based anticorrosion coating material with the rust construction of water band of the present embodiment, including following step
It is rapid:
(1) 53 parts of the epoxy resin of the Ultra-low molecular weight in component A, 9 parts of organic siliconresin, nano particle/graphene
1 part of composite material, 8.8 parts of aqueous phosphate chelate, 9 parts of barium sulfate, 9 parts of talcum powder, 9 parts of diamond dust, silicone resin 1
Part, 0.2 part of organic silicon defoamer, with Large-power High-Speed dispersion machine under conditions of 2000 revs/min, dispersion is wrapped after 1.5 hours
It is packed into library；
It (2) is that 9:1 uniformly mixes to get the product according to weight ratio by component A obtained and second group.
In the present embodiment, nanoparticle/graphene composite material the preparation method is as follows:
(1) preparation method of graphene oxide is the same as the step (1) in example IV；
(2) 30mg nano zircite is distributed to the second for the gamma-aminopropyl-triethoxy-silane that 50mL volume fraction is 2%
In alcoholic solution, 6mL deionized water is added dropwise at 90 DEG C of water-bath by ultrasonic 2h, reacts 10h, obtained product dehydrated alcohol and go from
Sub- water washs three times respectively, and functionalization zirconium oxide is obtained after freeze-drying；
(3) 40mg graphene oxide is distributed to 50mL volume fraction is 2% γ-glycidylpropyl methyl dimethoxy oxygen
In the alcohol solvent of base silane, ultrasonic 2h reacts 10h at 90 DEG C of water-bath, obtained product dehydrated alcohol and deionization moisture
It does not wash three times, functional graphene oxide is obtained after freeze-drying；
(4) 30mg functional graphene oxide is added to 6mLN, in dinethylformamide, 20mg is added in ultrasonic 2h
Functionalized nano particle, ultrasonic 2h react 12h at 90 DEG C of oil bath, obtain mixed solution；
(5) in mixed solution instill 1.5mL 40g/L sodium borohydride solution, obtained product dehydrated alcohol and go from
Sub- water washs respectively, and nanoparticle/graphene composite material is obtained after freeze-drying.
The performance test results of the present embodiment are as follows:
Embodiment three
A kind of graphene-based anticorrosion coating material with the rust construction of water band, including component A and component B.Its main component
By weight:
The component A each component are as follows: 8 parts of 55 parts of epoxy resin, organic siliconresin, the nano particle/stone of Ultra-low molecular weight
2 parts of black alkene composite material, 7 parts of aqueous phosphate chelate, 8 parts of barium sulfate, 8 parts of talcum powder, 10 parts of diamond dust, silicone resin
1.5 parts, 0.5 part of organic silicon defoamer；
The component B each component are as follows: 100 parts of cashew nut oil modified phenolic aldehyde polyimide resin.
Prepare the preparation method of the graphene-based anticorrosion coating material with the rust construction of water band of the present embodiment, including following step
It is rapid:
(1) 55 parts of the epoxy resin of the Ultra-low molecular weight in component A, 8 parts of organic siliconresin, nano particle/graphene
2 parts of composite material, 7 parts of aqueous phosphate chelate, 8 parts of barium sulfate, 8 parts of talcum powder, 10 parts of diamond dust, silicone resin 1.5
Part, 0.5 part of organic silicon defoamer, with Large-power High-Speed dispersion machine under conditions of 2500 revs/min, dispersion is packed after 1 hour
Storage；
It (2) is that 10:1 uniformly mixes to get the product according to weight ratio by component A obtained and second group.
In the present embodiment, nanoparticle/graphene composite material the preparation method is as follows:
(1) preparation method of graphene oxide is the same as the step (1) in example IV；
(2) 40mg nano silica is distributed to the gamma-aminopropyl-triethoxy-silane that 50mL volume fraction is 2%
In ethanol solution, 6mL deionized water is added dropwise at 90 DEG C of water-bath by ultrasonic 2h, reacts 10h, obtained product dehydrated alcohol and goes
Ionized water washs three times respectively, and functionalization zirconium oxide is obtained after freeze-drying；
(3) 40mg graphene oxide is distributed to γ-glycidylpropyl methyl dimethoxy that 40mL volume fraction is 2%
In the ethanol solution of oxysilane, 6mL deionized water is added dropwise at 90 DEG C of water-bath by ultrasonic 2h, reacts 10h, obtained product nothing
Water-ethanol and deionized water are washed three times respectively, and functional graphene oxide is obtained after freeze-drying；
(4) 30mg functional graphene oxide is added to 6mLN, in dinethylformamide, function is added in ultrasonic 2h
Change nano particle, ultrasonic 2h reacts 12h at 90 DEG C of oil bath, obtains mixed solution；
(5) hydrazine hydrate solution that 1.5mL 80wt% is instilled in mixed solution, obtained product dehydrated alcohol and goes
Ionized water washs respectively, and nanoparticle/graphene composite material is obtained after freeze-drying.
The performance test results of the present embodiment are as follows:
Example IV
A kind of graphene-based anticorrosion coating material with the rust construction of water band, including component A and component B.Its main component
By weight:
The component A each component are as follows: 9 parts of 53 parts of epoxy resin, organic siliconresin, the nano particle/stone of Ultra-low molecular weight
1 part of black alkene composite material, 8.8 parts of aqueous phosphate chelate, 9 parts of barium sulfate, 9 parts of talcum powder, 8.8 parts of diamond dust, siloxanes
1 part of resin, 0.4 part of organic silicon defoamer；
The component B each component are as follows: 100 parts of cashew nut oil modified phenolic aldehyde polyimide resin.
(1) 53 parts of the epoxy resin of the Ultra-low molecular weight in component A, 9 parts of organic siliconresin, nano particle/graphene
1 part of composite material, 8.8 parts of aqueous phosphate chelate, 9 parts of barium sulfate, 9 parts of talcum powder, 8.8 parts of diamond dust, silicone resin 1
Part, 0.4 part of organic silicon defoamer, with Large-power High-Speed dispersion machine under conditions of 2000 revs/min, dispersion is wrapped after 1.5 hours
It is packed into library；
It (2) is that 9.5:1 uniformly mixes to get the product according to weight ratio by component A obtained and second group.
In the present embodiment, nanoparticle/graphene composite material the preparation method is as follows:
(1) using natural flake graphite as raw material, graphene oxide is prepared using Hummers method is improved.Weigh 1.0g scale
Graphite, 3g potassium permanganate, 0.5g sodium nitrate are added sequentially in cooling kettle gallbladder, add 98% concentrated sulfuric acid of 30mL, are covered rapidly
Upper kettle cover is tightened, and refrigerator deepfreeze 30min is put into；Reaction kettle is taken out, 80 DEG C of baking oven reaction 10min are placed, after taking-up
It is cooled to room temperature；Product is poured into the beaker for filling 100ml deionized water, a certain amount of hydrogen peroxide is added dropwise until liquid becomes bright
Yellow or khaki；24 hours are stood, supernatant liquor is outwelled, first carries out 3 pickling with 5% HCl, then repeatedly washed
Its PH is washed until 5~7；After the centrifugation of acquired solution, the substance of bottom is high concentration graphene oxide, freeze-drying
After obtain graphene oxide.
(2) 30mg nano zircite is distributed to the 3- TSL 8330 that 50mL volume fraction is 2%
In ethanol solution, 6mL deionized water is added dropwise at 90 DEG C of water-bath by ultrasonic 2h, reacts 10h, obtained product dehydrated alcohol and goes
Ionized water washs three times respectively, and functionalization zirconium oxide is obtained after freeze-drying；
(3) 30mg graphene oxide is distributed to γ-glycidyl ether oxygen propyl trimethoxy that 50mL volume fraction is 2%
In the ethanol solution of base silane, 6mL deionized water is added dropwise at 90 DEG C of water-bath by ultrasonic 2h, reacts 10h, and obtained product is with anhydrous
Ethyl alcohol and deionized water are washed three times respectively, and functional graphene oxide is obtained after freeze-drying；
(4) 30mg functional graphene oxide is added to 6mLN, in dinethylformamide, 10mg is added in ultrasonic 2h
Functionalized nano particle, ultrasonic 2h react 12h at 90 DEG C of oil bath, obtain mixed solution；
(5) in mixed solution instill 1.5mL 80wt% hydrazine hydrate solution, obtained product dehydrated alcohol and go from
Sub- water washs respectively, and nanoparticle/graphene composite material is obtained after freeze-drying.
The performance test results of the present embodiment are as follows:
Embodiment five
A kind of graphene-based anticorrosion coating material with the rust construction of water band, including component A and component B.Its main component
By weight:
The component A each component are as follows: 10 parts of 50 parts of epoxy resin, the organic siliconresin of Ultra-low molecular weight, nano particle/
1.5 parts of graphene composite material, 7 parts of aqueous phosphate chelate, 9.9 parts of barium sulfate, 9.8 parts of talcum powder, 9.8 parts of diamond dust,
1.5 parts of silicone resin, 0.5 part of organic silicon defoamer；
The component B each component are as follows: 100 parts of cashew nut oil modified phenolic aldehyde polyimide resin.
Prepare the preparation method of the graphene-based anticorrosion coating material with the rust construction of water band of the present embodiment, including following step
It is rapid:
(1) 50 parts of the epoxy resin of the Ultra-low molecular weight in component A, 10 parts of organic siliconresin, nano particle/graphite
1.5 parts of alkene composite material, 7 parts of aqueous phosphate chelate, 9.9 parts of barium sulfate, 9.8 parts of talcum powder, 9.8 parts of diamond dust, silicon oxygen
1.5 parts of alkane resin, 0.5 part of organic silicon defoamer, with Large-power High-Speed dispersion machine under conditions of 1500 revs/min, dispersion 2 is small
When after be packed and stored；
It (2) is that 8:1 uniformly mixes to get the product according to weight ratio by component A obtained and second group.
In the present embodiment, nanoparticle/graphene composite material the preparation method is as follows:
(1) preparation method of graphene oxide is the same as the step (1) in example IV；
(2) 60mg nano-titanium oxide is distributed to the second for the gamma-aminopropyl-triethoxy-silane that 90mL volume fraction is 2%
In alcoholic solution, 12mL deionized water is added dropwise at 90 DEG C of water-bath by ultrasonic 2h, reacts 10h, obtained product dehydrated alcohol and go from
Sub- water washs three times respectively, and functionalization titanium oxide is obtained after freeze-drying；
(3) 30mg graphene oxide is distributed to γ-glycidylpropyl methyl dimethoxy that 50mL volume fraction is 2%
In the ethanol solution of oxysilane, 6mL deionized water is added dropwise at 90 DEG C of water-bath by ultrasonic 2h, reacts 10h, obtained product nothing
Water-ethanol and deionized water are washed three times respectively, and functional graphene oxide is obtained after freeze-drying；
(4) 30mg functional graphene oxide is added to 5.5mLN, in dinethylformamide, ultrasonic 2h is added
15mg functionalized nano particle, ultrasonic 2h react 12h at 90 DEG C of oil bath, obtain mixed solution；
(5) in mixed solution instill 1.0mL 40g/L sodium borohydride solution, obtained product dehydrated alcohol and go from
Sub- water washs respectively, and nanoparticle/graphene composite material is obtained after freeze-drying.
The performance test results of the present embodiment are as follows:
Claims (9)
1. a kind of graphene-based anticorrosion coating material with the rust construction of water band, which is characterized in that including component A and component B, institute
The component A stated is prepared by each component of following weight parts:
5-10 parts of 45-55 parts of epoxy resin, organic siliconresin, the nanoparticle/graphene composite material 0.5-2 of Ultra-low molecular weight
Part, 5-10 parts of aqueous phosphate chelate, 5-10 parts of barium sulfate, 5-10 parts of talcum powder, 5-10 parts of diamond dust, silicone resin 1-
1.5 0.1-0.5 parts of part, organic silicon defoamer；
The component B are as follows: 100 parts of cashew nut oil modified phenolic aldehyde polyimide resin；
The preparation method of the nanoparticle/graphene composite material, comprising the following steps:
(1) using natural flake graphite as raw material, graphene oxide is prepared using Hummers method is improved；
(2) nano particle is distributed in the ethanol solution containing amino silicane coupling agent that volume fraction is 2%, ultrasonic 2h, water-bath
Deionized water is added dropwise at 90 DEG C, reacts 10h, obtained product dehydrated alcohol and deionized water are washed three times respectively, and freezing is dry
Functionalized nano particle is obtained after dry；
(3) graphene oxide prepared by step (1) is distributed to the ethyl alcohol containing epoxy silane coupling that volume fraction is 2%
In solution, deionized water is added dropwise at 90 DEG C of water-bath by ultrasonic 2h, reacts 10h, obtained product dehydrated alcohol and deionization moisture
It does not wash three times, functional graphene oxide is obtained after freeze-drying；
(4) functional graphene oxide made from step (3) is added in n,N-Dimethylformamide, ultrasonic 2h, step is added
Suddenly the functionalized nano particle of (2) preparation, ultrasonic 2h react 12h at 90 DEG C of oil bath, obtain mixed solution；
(5) reducing agent solution is instilled in mixed solution, obtained product dehydrated alcohol and deionized water are washed three times respectively,
Graphene/nanometer particulate composite is obtained after freeze-drying.
2. the graphene-based anticorrosion coating material as described in claim 1 with the rust construction of water band, it is characterised in that: its preparation side
Method includes the following steps:
(1) according to the parts by weight of each component of component A, each substance is weighed, the Large-power High-Speed point of all components in component A
Machine is dissipated under conditions of 1500-2500 revs/min, and dispersion is packed and stored after 1-2 hours；
It (2) is that 7-10:1 uniformly mixes to get the product according to weight ratio by component A obtained and component B.
3. the graphene-based anticorrosion coating material as described in claim 1 with the rust construction of water band, it is characterized in that: nano particle/
In the preparation method of graphene composite material, 3- aminopropyl front three is selected containing amino silicane coupling agent described in step (2)
Oxysilane, gamma-aminopropyl-triethoxy-silane, N- aminoethyl-gamma-aminopropyl-triethoxy-silane, N-(β-aminoethyl)-
One of γ-aminopropyltrimethoxysilane, N- β-(aminoethyl)-γ-aminopropyltriethoxy dimethoxysilane.
4. the graphene-based anticorrosion coating material as described in claim 1 with the rust construction of water band, it is characterized in that: nano particle/
In the preparation method of graphene composite material, nano particle described in step (2) selects nano zircite, nanometer titanium dioxide
One of silicon, nano-titanium dioxide, nano aluminium oxide.
5. the graphene-based anticorrosion coating material as described in claim 1 with the rust construction of water band, it is characterized in that: nano particle/
In the preparation method of graphene composite material, nano particle described in step (2) and the amount ratio containing amino silicane coupling agent
For 1-5g:100mL.
6. the graphene-based anticorrosion coating material as described in claim 1 with the rust construction of water band, it is characterized in that: nano particle/
In the preparation method of graphene composite material, nano particle described in step (2) and the amount ratio of the deionized water of dropwise addition are
1-2g:200mL.
7. the graphene-based anticorrosion coating material as described in claim 1 with the rust construction of water band, it is characterized in that: nano particle/
In the preparation method of graphene composite material, γ-glycidol ether is selected containing epoxy silane coupling described in step (3)
Oxygen propyl trimethoxy silicane, γ-glycidylpropyl methyl dimethoxysilane, three second of 3- glycydoxy
One of oxysilane, 2- (3,4- 7-oxa-bicyclo[4.1.0 base) ethyl trimethoxy silane.
8. the graphene-based anticorrosion coating material as described in claim 1 with the rust construction of water band, it is characterized in that: nano particle/
In the preparation method of graphene composite material, graphene oxide described in step (3) and the use containing epoxy silane coupling
Amount is than being 1-5g:100mL；Graphene oxide described in step (3) and the amount ratio of the deionized water of dropwise addition are 1-2g:
200mL。
9. the graphene-based anticorrosion coating material as described in claim 1 with the rust construction of water band, it is characterized in that: nano particle/
In the preparation method of graphene composite material, functional graphene oxide and n,N-Dimethylformamide described in step (4)
Mass volume ratio be 1-2g:200mL；The weight of functional graphene oxide and functionalized nano particle described in step (4)
Amount is than being 2-3:1；Reducing solution described in step (5) selects one of hydrazine hydrate, sodium borohydride；Described in step (5)
Mixed solution and reducing solution volume ratio be 3-5:1.
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| CN109486358B (en) * | 2018-11-30 | 2020-11-13 | 郑州工程技术学院 | Environment-friendly coating and preparation method thereof |
| CN109761584B (en) * | 2018-12-29 | 2022-01-07 | 江南大学 | Graphene oxide hybrid aluminum oxide corrosion-resistant ceramic coating and preparation method thereof |
| CN110305580B (en) * | 2019-05-06 | 2021-06-15 | 吉林大学 | Graphene-based hydrophobic anticorrosive coating and preparation method and application thereof |
| CN110564262A (en) * | 2019-09-05 | 2019-12-13 | 天恒涂料有限公司 | Graphene-coated titanium nano heavy-duty anticorrosive paint and preparation method thereof |
| CN117126579A (en) * | 2023-07-10 | 2023-11-28 | 泉州职业技术大学 | Graphene marine anticorrosive paint and preparation method thereof |
| CN117264484A (en) * | 2023-10-23 | 2023-12-22 | 国网四川电力送变电建设有限公司 | Corrosion-resistant and wear-resistant coating with low surface energy, and preparation method and application thereof |
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| CF01 | Termination of patent right due to non-payment of annual fee |