CN108795283A - A kind of preparation method and application of free-floride room temperature curing graphene-organic siliconresin super hydrophobic coating - Google Patents
A kind of preparation method and application of free-floride room temperature curing graphene-organic siliconresin super hydrophobic coating Download PDFInfo
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- CN108795283A CN108795283A CN201810661701.8A CN201810661701A CN108795283A CN 108795283 A CN108795283 A CN 108795283A CN 201810661701 A CN201810661701 A CN 201810661701A CN 108795283 A CN108795283 A CN 108795283A
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- 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
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
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- 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
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- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
- C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/70—Additives characterised by shape, e.g. fibres, flakes or microspheres
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- 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
Abstract
The present invention relates to a kind of preparation method and applications of floride-free room temperature curing graphene-organic siliconresin super hydrophobic coating.Organic fluoride is used by limitation in the world since its superpower chemical stability causes to be difficult to decompose.Graphene is combined with organic siliconresin by physics mode and chemical mode by the present invention, can be obtained the good super-hydrophobic coat of storage stability by simple process.There is the super-hydrophobic coat of gained of the invention good mechanical performance and chemical stability, static water droplet contact angle to be more than 150 °, have certain electric conductivity, have a extensive future in waterproof anti-ice, the heating that is powered, anti-electromagnetic shielding and antistatic field.
Description
Technical field
The invention belongs to super-hydrophobic coat technical fields, and in particular to a kind of free-floride room temperature curing graphene-organosilicon tree
The preparation method and application of fat super hydrophobic coating.
Background technology
Super hydrophobic surface refers generally to water droplet and is in contact with it angle more than 150 °, and roll angle is less than 10 ° of surface.It has from clear
The good characteristics such as clean, anti-adhesive, waterproof so that super hydrophobic material is in waterproof clothes, exterior coating, electronic component, grease point
Very extensive application prospect is shown from fields such as, biological medicines.To ask hydrophobic effect, the preparation of existing super hydrophobic surface
Method is mostly to add the organic fluoride-containing compound of extremely low surface energy.However due to fluoro- carbon key in organic fluoride-containing compound structure
Bond energy is extremely strong so that the chemical property of this substance is extremely stablized, and high temperature, illumination, most chemical reaction, micro- can be subjected to
The metabolism of biological effect and animals and plants.Ecological environment problem and the health danger that may cause in view of substance of this kind
Evil has had Countries and area to be included in some fluorinated organic compounds and be forbidden to use list.In addition, coating surface is received
Micro-structure is easily destroyed, its ultra-hydrophobicity is made to be difficult to keep in use.Super-hydrophobic coat is prepared at present simultaneously
Method is typically more complicated, and process conditions are harsher, it is difficult to realize live large area application.Therefore, invent it is a kind of floride-free and
Performance is stable, can post coat, the preparation of simple and practicable super-hydrophobic coat and application method, to pushing super-hydrophobic coat in reality
Application in border production, life is of great significance and more practical value.
Graphene has excellent mechanical property, can build stable nano-micro structure, but graphene chemical inertness, Wu Fahe
Organic siliconresin uniformly mixes on molecular scale, instead results in coating mechanical properties decrease；But the active oxidation of chemical property
Graphene hydrophily is too strong, causes coating hydrophobic effect bad.At present the technical solution adopted is that by graphene oxide fluorination
Reason is to reduce its surface energy, but this can bring environmental problem as stated in the background art.In addition, existing prepare super-hydrophobic painting
The method of layer is typically more complicated, and process conditions are harsher, it is difficult to realize live large area application.
Invention content
That the purpose of the present invention is to provide a kind of performances is stable, can post coat, simple and practicable floride-free room temperature curing stone
The preparation method and application of black alkene-organic siliconresin super hydrophobic coating.Wherein, graphene provides excellent mechanical property and structure
Nano-micro structure, organic siliconresin provide splendid hydrophobic and film-formation result.
It is to solve the above-mentioned problems the technical scheme is that such：A kind of free-floride room temperature curing graphene-is organic
The preparation method of silicones super hydrophobic coating is reacted with silane coupling agent first with the active graphene oxide of chemical property, is made
Graphene surface silanization promotes the compatibility with organic siliconresin；The graphene of silanization is mixed with organic siliconresin again,
Film, dry solidification obtain graphene-organic siliconresin super-hydrophobic coat.
Specifically include following steps：
A, graphene oxide powder and silane coupling agent are scattered in solvent, stir and ultrasound to be allowed to evenly dispersed 0.5-7 small
The slurries filtration is drying to obtain silanization graphene by Shi Hou.
Wherein：Solvent is one kind in the organic solvents such as alcohol, ether, dimethylacetylamide, chloroform or N-Methyl pyrrolidone
Or several mixing.
Silane coupling agent is gamma-aminopropyl-triethoxy-silane, γ-（The third oxygen of 2,3- epoxies）Propyl trimethoxy silicane,
N-（β-aminoethyl）- γ-aminopropyltriethoxies dimethoxysilane or N-（β-aminoethyl）In γ-aminopropyltrimethoxysilane
One or more of mixing.
It counts in mass ratio, 1-10 parts of graphene oxide, 1~50 part of silane coupling agent, 10~2000 parts of solvent；
Preferably, graphene oxide 1-5 parts, 1~25 part of silane coupling agent, 30~500 parts of solvent；More preferably
It is 1-5 parts of graphene oxide, 1~30 part of silane coupling agent, 20~200 parts of solvent.
B, the silanization graphene in A is added in organosilicon, strong stirring is allowed to evenly dispersed, and obtaining graphene-has
Machine silicon slurry.Organosilicon therein is one or more of in hydroxy silicon oil, containing hydrogen silicone oil, vinyl silicone oil or ethyoxyl silicone oil
Mixing.It counts in mass ratio, 1-20 parts of silanization graphene, 1~100 part of organosilicon；Wherein it is preferred that silanization graphene 1-
10 parts, 1-20 parts of organosilicon.
C, graphene-organosilicon syrup in B is added in catalyst, adds solvent to adjust viscosity, stirs evenly i.e.
Obtain graphene-organic siliconresin super hydrophobic coating.Wherein catalyst, graphene-organosilicon syrup and solvent are counted in mass ratio, are urged
1-10 parts of agent, 10~500 parts of graphene-organosilicon syrup, 100~3000 parts of solvent；Wherein catalyst is platinum catalyst, two
Dibutyl tin laurate, stannous octoate, acids, bases or salt；Solvent is one in ester, ether, ketone, alcohol, aromatic hydrocarbon or alkane
Kind or several mixing.
Coating in C is coated on substrate surface, waits spontaneously drying solidification to get the super-hydrophobic painting of graphene-organic siliconresin
Layer.
The base material is metal material, inorganic non-metallic material（Such as glass, ceramics）, high molecular material（Such as plastics）,
The solid materials such as fabric or composite material.
Specifically, the present invention provides a kind of preparations of floride-free room temperature curing graphene-organic siliconresin super hydrophobic coating
Method includes the following steps：
1, graphene oxide powder and silane coupling agent are scattered in solvent D, stir and ultrasound is allowed to evenly dispersed, then will
Mixture filtration drying obtains silanization graphene.
2, the silanization graphene in A is added in organosilicon, is strongly allowed to evenly dispersed, obtain graphene-organosilicon
Slurry.
3, graphene-organosilicon syrup in B is added in catalyst, adds solvent E to adjust viscosity, stirs evenly to obtain stone
Black alkene-organic siliconresin super hydrophobic coating.
Further, the graphene oxide powder and silane coupling agent and solvent D, are counted, graphite oxide in mass ratio
1-10 parts of alkene, 1~50 part of silane coupling agent, 10-2000 parts of solvent D；The silane coupling agent is vinyl tri-alkoxy silicon
Alkane, gamma-aminopropyl-triethoxy-silane, γ-（The third oxygen of 2,3- epoxies）Propyl trimethoxy silicane, N-（β-aminoethyl）- γ-ammonia
Hydroxypropyl methyl dimethoxysilane or N-（β-aminoethyl）One or more of mixing in γ-aminopropyltrimethoxysilane；Institute
It is organic solvent to state solvent D, is specifically as follows in alcohol, ether, dimethylacetylamide, chloroform or N-Methyl pyrrolidone a kind of or several
The mixing of kind.
Further, the silanization graphene and organosilicon are counted in mass ratio, 1-20 parts of silanization graphene, organosilicon 1
~100 parts；The organosilicon is one or more of in hydroxy silicon oil, containing hydrogen silicone oil, vinyl silicone oil or ethyoxyl silicone oil mixes
It closes.
Further, the catalyst, graphene-organosilicon syrup and solvent E are counted in mass ratio, 1-10 parts of catalyst,
Graphene -10-500 parts of organosilicon syrup, 100-3000 parts of solvent E；The catalyst is platinum catalyst, two fourth of tin dilaurate
Base tin or stannous octoate；The solvent E is mixing one or more of in ester, ether, ketone, alcohol, aromatic hydrocarbon or alkane.
Further, the graphene-organosilicon super hydrophobic coating is coated on substrate surface, waits spontaneously drying solidification, i.e.,
Obtain graphene-organic siliconresin super-hydrophobic coat.The base material is metal material, inorganic non-metallic material（Such as glass, ceramics）,
High molecular material（Such as plastics）, the solid materials such as fabric or composite material.
Organic siliconresin is that a kind of alternately linked by silicon atom and oxygen atom forms skeleton, then by different organic groups with
The general designation of the polymer of silicon atom connection.Due to the unique texture of organosilicon, inorganic material and the performance of organic material have been had both,
In addition to the fundamental propertys such as low with surface tension, viscosity-temperature coefficient is small, compressibility is high, gas permeability is high, also have high-low temperature resistant,
The excellent specific properties such as electric insulation, resistance to oxidation stability, weatherability, fire retardant, hydrophobic, corrosion-resistant, non-toxic and tasteless and physiological inertia.
Wherein single-component silicon rubber is easy-to-use, has good adhesive property and solidfied material electrical insulation properties；Have simultaneously moisture-proof
The functions such as shockproof, arc resistant, ageing-resistant, moisture-proof.Graphene is a kind of novel carbon nanomaterial, has specific surface area height, connects
The features such as contacting surface product is big, superficial attractive forces are strong.
The beneficial effects of the invention are as follows：Graphene is incorporated in substrate surface with organic siliconresin and forms two-dimension plane structure,
The adsorption capacity for enhancing coating and substrate, makes coating more even compact, bond strength higher, improves the toughness, wear-resisting of coating
Property and antiseptic property.In addition, the unique two-dimensional slice structure of graphene helps to construct coarse nano-micro structure in coating surface,
In conjunction with the distinctive physical and chemical performance of organic siliconresin, the super-hydrophobic painting of excellent physical property and stable chemical performance is constructed
Layer.
Description of the drawings
Fig. 1 is the hydrophobicity experiment effect comparison diagram of metal material.
The copper sheet hydrophobicity effect figure of the non-coating in left side；Right side is to be coated with graphene-organic siliconresin super-hydrophobic coat
Copper sheet hydrophobicity effect figure.
Specific implementation mode
Below in conjunction with attached drawing embodiment, present invention is further described in detail.
In order to make the technical means, the creative features, the aims and the efficiencies achieved by the present invention be easy to understand, tie below
Conjunction is specifically illustrating, and the present invention is further explained.
Embodiment 1, a kind of preparation method of floride-free room temperature curing graphene-organic siliconresin super-hydrophobic coat
10g graphene oxide powders and 10g gamma-aminopropyl-triethoxy-silanes are scattered in 300g ethyl alcohol, simultaneously ultrasound 1 is stirred
Hour, filtration drying obtains silanization graphene.10g silanization graphenes are added in 30g hydroxy silicon oils, strength mechanical agitation is extremely
Uniformly, graphene-organosilicon syrup is obtained.0.4g dibutyl tin laurates are added, it is viscous to adjust to add 800g butyl acetates
Degree stirs evenly up to graphene-organic siliconresin super hydrophobic coating.By graphene-organic siliconresin super hydrophobic coating spraying
To glass pane surface, dry solidification one day is to get graphene-organic siliconresin super-hydrophobic coat under natural environment.
In all embodiments, in addition to using spraying method, it can also be that blade coating, spin coating, drop coating, dip-coating, brushing etc. are available
Any coating method.
Embodiment 2, a kind of preparation method of floride-free room temperature curing graphene-organic siliconresin super-hydrophobic coat
By 10g graphene oxide powders, 10g gamma-aminopropyl-triethoxy-silanes and 10g vinyl trialkyl oxysilanes are scattered in
In 1000g chloroforms, stir and 2 hours ultrasonic, filtration drying obtains silanization graphene.10g silanization graphenes addition 15g is contained
In hydrogen silicone oil and 25g vinyl silicone oils, strength mechanical agitation obtains graphene-organosilicon syrup to uniform.0.25g platinum is added to urge
Agent adds 100g butanol to adjust viscosity, stirs evenly up to graphene-organic siliconresin super hydrophobic coating.By graphite
Alkene-organic siliconresin super hydrophobic coating is brushed to copper sheet surface, and dry solidification one day is organic to get graphene-under natural environment
Silicones super-hydrophobic coat（See Fig. 1）.
Embodiment 3, a kind of preparation method of floride-free room temperature curing graphene-organic siliconresin super-hydrophobic coat
By 10g graphene oxide powders, 10gN-（β-aminoethyl）γ-aminopropyltrimethoxysilane is scattered in 500g dimethyl
In acetamide, stir and 3 hours ultrasonic, filtration drying obtains silanization graphene.30g ethoxies are added in 10g silanization graphenes
In base silicone oil and 70g hydroxy silicon oils, strength mechanical agitation obtains graphene-organosilicon syrup to uniform.1g stannous octoates are added,
500g hexamethylenes are added to adjust viscosity, are stirred evenly up to graphene-organic siliconresin super hydrophobic coating.By graphene-
Organic siliconresin super hydrophobic coating is brushed to aluminium oxide ceramics plate surface, and dry solidification one day is to get graphene-under natural environment
Organic siliconresin super-hydrophobic coat.
Embodiment 4, a kind of preparation method of floride-free room temperature curing graphene-organic siliconresin super-hydrophobic coat
By 10g graphene oxide powders, 30g γ-（The third oxygen of 2,3- epoxies）Propyl trimethoxy silicane is scattered in 1000g toluene
In, it stirs and 4 hours ultrasonic, filtration drying obtains silanization graphene.50g ethyoxyl silicone oil is added in 10g silanization graphenes
In, strength mechanical agitation obtains graphene-organosilicon syrup to uniform.0.5g dibutyl tin laurates are added, add 800g
Tetrahydrofuran is stirred evenly with adjusting viscosity up to graphene-organic siliconresin super hydrophobic coating.By graphene-organosilicon tree
Fat super hydrophobic coating is brushed to aluminium material surface, and dry solidification one day is super-hydrophobic to get graphene-organic siliconresin under natural environment
Coating.
Comparative example 1
This comparative example is differed only in embodiment 1：
0.4g dibutyl tin laurates are added without, viscosity is directly adjusted, are stirred evenly super thin up to graphene-organic siliconresin
Water paint.
The coating is sprayed into glass pane surface using 1 same method of embodiment, places one day, is thrown away as liquid under natural environment
State, coating do not cure.
The explanation of above example is only intended to facilitate the understanding of the method and its core concept of the invention.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 improvement and modification are also fallen within the protection scope of the claims of the present invention.
The foregoing description of the disclosed embodiments enables those skilled in the art to implement or use the present invention.
Various modifications to these embodiments will be apparent to those skilled in the art, as defined herein
General Principle can be realized in other embodiments without departing from the spirit or scope of the present invention.Therefore, of the invention
It is not intended to be limited to the embodiments shown herein, and is to fit to and the principles and novel features disclosed herein phase one
The widest range caused.
Claims (10)
1. a kind of preparation method of free-floride room temperature curing graphene-organic siliconresin super hydrophobic coating, which is characterized in that including with
Lower step：
Step A, graphene oxide powder and silane coupling agent are scattered in solvent D, are uniformly dispersed, then filter mixture
Dry silanization graphene；
Step B, the silanization graphene in step A is added in organosilicon, is uniformly dispersed, obtain graphene-organosilicon syrup；
Step C, catalyst is added in graphene-organosilicon syrup made from step B, adds solvent E to adjust viscosity, stirs
Mix uniform graphene-organic siliconresin super hydrophobic coating；The catalyst is platinum catalyst, dibutyl tin laurate or pungent
Sour stannous.
2. a kind of preparation side of floride-free room temperature curing graphene-organic siliconresin super hydrophobic coating according to claim 1
Method, which is characterized in that graphene oxide powder, silane coupling agent and the solvent D, in parts by mass, graphene oxide 1-
10 parts, 1~50 part of silane coupling agent, 10-2000 parts of solvent D.
3. a kind of preparation of floride-free room temperature curing graphene-organic siliconresin super hydrophobic coating according to claim 1 or 2
Method, which is characterized in that the silane coupling agent is gamma-aminopropyl-triethoxy-silane, γ-（The third oxygen of 2,3- epoxies）Propyl three
Methoxy silane, N-（β-aminoethyl）- γ-aminopropyltriethoxies dimethoxysilane, N-（β-aminoethyl）- γ-aminopropyl front threes
One or more of mixing in oxysilane.
4. a kind of preparation of floride-free room temperature curing graphene-organic siliconresin super hydrophobic coating according to claim 1 or 2
Method, which is characterized in that the solvent D is one or more of in alcohol, ether, dimethylacetylamide, chloroform, N-Methyl pyrrolidone
Mixing.
5. a kind of preparation side of floride-free room temperature curing graphene-organic siliconresin super hydrophobic coating according to claim 1
Method, which is characterized in that the silanization graphene and organosilicon are counted in mass ratio, 1-20 parts of silanization graphene, organosilicon 1~
100 parts.
6. a kind of preparation of floride-free room temperature curing graphene-organic siliconresin super hydrophobic coating according to claim 1 or 5
Method, which is characterized in that the organosilicon be it is a kind of in hydroxy silicon oil, containing hydrogen silicone oil, vinyl silicone oil or ethyoxyl silicone oil or
Several mixing.
7. a kind of preparation side of floride-free room temperature curing graphene-organic siliconresin super hydrophobic coating according to claim 1
Method, which is characterized in that catalyst, graphene-organosilicon syrup and the solvent E is counted in mass ratio, 1-10 parts of catalyst, stone
Black alkene -10-500 parts of organosilicon syrup, 100-3000 parts of solvent E.
8. a kind of floride-free room temperature curing graphene-organic siliconresin super hydrophobic coating according to one of claim 1 to 7
Preparation method, which is characterized in that the solvent E is the mixing of one or more of ester, ether, ketone, alcohol, aromatic hydrocarbon, alkane.
9. a kind of preparation method of free-floride room temperature curing graphene-organic siliconresin super-hydrophobic coat, it is characterised in that by right
It is required that floride-free room temperature curing graphene-organic siliconresin super hydrophobic coating prepared by one of 1-8 is coated on substrate surface, wait for certainly
Right dry solidification is to get graphene-organic siliconresin super-hydrophobic coat.
10. a kind of preparation method without fluorine graphene-organosilicon super-hydrophobic coat according to claim 9, feature
It is, the base material is metal material, inorganic non-metallic material, high molecular material, fabric or composite material.
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| CN110681549A (en) * | 2019-09-24 | 2020-01-14 | 西安交通大学 | High-heat-conductivity super-hydrophobic flue gas condensation heat exchange surface and preparation method and device thereof |
| CN113337120A (en) * | 2021-06-10 | 2021-09-03 | 山西利协科技股份有限公司 | Preparation method of graphene radiation-proof material and radiation-proof garment |
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| CN109762464A (en) * | 2019-01-28 | 2019-05-17 | 新辉（中国）新材料有限公司 | Hydrophobic coating material of high-hardness high-light pool degree of room temperature curing and preparation method thereof |
| CN109762464B (en) * | 2019-01-28 | 2021-04-30 | 新辉（中国）新材料有限公司 | Room-temperature-cured high-hardness high-glossiness hydrophobic coating material and preparation method thereof |
| CN110681549A (en) * | 2019-09-24 | 2020-01-14 | 西安交通大学 | High-heat-conductivity super-hydrophobic flue gas condensation heat exchange surface and preparation method and device thereof |
| CN113337120A (en) * | 2021-06-10 | 2021-09-03 | 山西利协科技股份有限公司 | Preparation method of graphene radiation-proof material and radiation-proof garment |
| CN114323852A (en) * | 2021-12-27 | 2022-04-12 | 山东大学 | Preparation method and application of laser-induced graphene without pinning effect |
| CN114323852B (en) * | 2021-12-27 | 2023-08-29 | 山东大学 | Preparation method and application of laser-induced graphene without pinning effect |
| CN115434044A (en) * | 2022-11-07 | 2022-12-06 | 江苏恒力化纤股份有限公司 | Solvent-free bi-component spinning oil agent and preparation method and application thereof |
| CN116589878A (en) * | 2023-07-19 | 2023-08-15 | 北京碧海云智新材料技术有限公司 | Long-acting self-cleaning graphene ceramic water paint and preparation method and application thereof |
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Application publication date: 20181113 |