CN109354963A - A kind of corrosion-resistant super hydrophobic coating and its preparation method and application - Google Patents
A kind of corrosion-resistant super hydrophobic coating and its preparation method and application Download PDFInfo
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- CN109354963A CN109354963A CN201811339911.1A CN201811339911A CN109354963A CN 109354963 A CN109354963 A CN 109354963A CN 201811339911 A CN201811339911 A CN 201811339911A CN 109354963 A CN109354963 A CN 109354963A
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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
- C09D153/00—Coating compositions based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
- C09D153/02—Vinyl aromatic monomers and conjugated dienes
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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
-
- 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
- C09D5/16—Antifouling paints; Underwater paints
- C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
- C09D5/1612—Non-macromolecular compounds
- C09D5/1618—Non-macromolecular compounds inorganic
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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
- 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
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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
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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)
- Inorganic Chemistry (AREA)
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Abstract
The invention discloses a kind of corrosion-resistant super hydrophobic coatings and its preparation method and application, the coating includes the raw material of following parts by weight: 0.8-1.2 parts of the SBS resin (styrene-butadiene-styrene triblock copolymer) of industrial mass production, 0.01-0.15 parts of natural rubber, 10-30 parts of solvent, 0.1-2.0 parts of silane coupler modified nano silicon dioxide sol, 2.0-8.0 parts of nano-titanium dioxide；Preparation method includes: that SBS resin and natural rubber are dissolved in solvent, and stirring adds modified silicon dioxide sol and nano-titanium dioxide, is stirred at room temperature to obtain the final product；The contact angle of gained coating is greater than 150°, roll angle is less than 6°, (3.5%NaCl) is impregnated 10 days through salt water, and coating still has super-hydrophobicity.The present invention passes through modified silicon dioxide sol and nano-titanium dioxide modified synergic, the multiple dimensioned coarse structure of coating surface is moulded, hydrophobic performance is excellent and stablizes, while having both good high temperature resistance, ageing-resistant performance and mechanical performance, preparation method is simple, has a extensive future.
Description
Technical field
The present invention relates to technical field of paint preparation, more particularly to a kind of corrosion-resistant super hydrophobic coating and its preparation
Methods and applications.
Background technique
Super-hydrophobic automatic cleaning surface, which refers to, is greater than 150 ° and surface of the roll angle less than 10 ° with the contact angle of water droplet, has
The material of super hydrophobic surface has extensive practical application in industrial and agricultural production and daily life, such as preventing for glass surface
Anticorrosion, the antifouling of fabric, water-oil separating and the microfluid transport of mist, automatically cleaning construction material, submerged structure and sail body
Deng.
In recent years, with the further investigation to super-hydrophobic coat, the preparation method of super-hydrophobic bionic coating emerges one after another, this
Outside, it is unfolded about the research of the preparation method of super-hydrophobic coat mainly around following two points: is on the one hand how to mould solid table
On the other hand the multiple dimensioned coarse structure in face is then how to reduce the surface energy of the surface of solids.
So far, existing due to many although there are many material system of super-hydrophobic bionic coating and preparation method
The preparation cost of some super hydrophobic coatings is generally higher, and preparation process is complicated；In addition, field operation experiences show it is existing
There is also bad mechanical property (including the adhesive force between substrate, surface hardness and wearability etc.) and hydrophobicitys for super hydrophobic coating
The problems such as easily losing, comprehensive performance needs to further increase.
In conclusion, by selecting suitable material system, improving preparation process how on existing Research foundation, mentioning
For a kind of preparation method is simple, technique is controllable, it is low in cost and have both excellent hydrophobic performance, corrosion resistance, mechanical performance and
Super hydrophobic coating of weather resistance and preparation method thereof has important theoretical and practical significance.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of corrosion-resistant super hydrophobic coating and preparation method thereof and answer
With the hydrophobic performance of obtained coating material is excellent, and performance is stablized, while having both good high temperature resistance, ageing-resistant
Performance and mechanical performance, comprehensive performance are substantially better than the coating of SBS resin and natural rubber.
In order to achieve the above objectives, the present invention adopts the following technical scheme:
A kind of corrosion-resistant super hydrophobic coating, the raw material including following parts by weight: the SBS resin 0.8- of industrial mass production
1.2 parts, 0.01-0.15 parts of natural rubber, 10-30 parts of solvent, silane coupler modified nano silicon dioxide sol 0.1-2.0
Part, 2.0-8.0 parts of nano-titanium dioxide.Preferably, the parts by weight of each raw material are as follows: 0.8-1.2 parts of SBS resin, natural rubber
0.05-0.10 parts of glue, 15-25 parts of solvent, 1.0-2.0 parts of silane coupler modified nano silicon dioxide sol, nano-silica
Change titanium 2.0-8.0 parts.
In the above-mentioned technical solutions, the partial size of the silane coupler modified nano silicon dioxide sol is 20-
130nm；The partial size of the nano-titanium dioxide is 20-120nm.
In the above-mentioned technical solutions, the solvent of the silane coupler modified nano silicon dioxide sol is toluene, two
One of toluene and methyl ethyl ketone, colloidal sol solid content are 5-30%.Preferably, the silane coupler modified nanometer titanium dioxide
The partial size of silica solution is 20-55nm, solid content 16-35%.
Preferably, in the above-mentioned technical solutions, the partial size of the nano-titanium dioxide is 20-75nm.
In the above-mentioned technical solutions, the solvent is in toluene, dimethylbenzene, ethyl acetate, butyl acetate, tetrahydrofuran etc.
It is one or more.
In the above-mentioned technical solutions, the modified silicon dioxide sol the preparation method is as follows:
The nano silicon dioxide sol of various partial sizes, surface containing great amount of hydroxy group is synthesized (with ethyl orthosilicate with Stober method
For silicon source, ammonium hydroxide is catalyst, and nano silicon dioxide sol is synthesized in METHANOL MEDIUM)；Then using silane coupling agent (as just
Octyl trimethoxy silane, n-hexyl trimethoxy silane, dodecyltrimethoxysilane, hexadecyl trimethoxy silane
Deng) modified to nano silica progress surface.
The preparation method of the above-mentioned corrosion-resistant super hydrophobic coating of the present invention, key step include:
S1, SBS resin, natural rubber are mixed according to the ratio with solvent, obtained SBS resin/natural rubber is stirred at room temperature
Sol solution；
S2, in proportion by modified silicon dioxide sol and nano-titanium dioxide be added to SBS resin obtained in step S1/
In natural rubber solution, it is stirred at room temperature up to corrosion-resistant super hydrophobic coating.
In the above-mentioned technical solutions, in step S2, the mixing time is 30-120min.
The present invention also provides a kind of corrosion-resistant super-hydrophobic coatings, use the corrosion-resistant super hydrophobic coating system of painting of the present invention
At the coating contact angle is greater than 150 °, and roll angle is less than 6 °；Preferably, (3.5%NaCl) is impregnated 10 days through salt water, coating
Still there is super-hydrophobicity.
Compared with prior art, the beneficial effects of the present invention are:
(1) corrosion-resistant super hydrophobic coating provided by the present invention passes through using through silane coupler modified hydrophobic nano
Silicon dioxide gel and nano-titanium dioxide modified synergic SBS resin/natural rubber, the hydrophobic performance of obtained coating material
It is excellent, and performance is stablized, while having both good high temperature resistance, ageing-resistant performance and mechanical performance, comprehensive performance is obviously excellent
In SBS resin and natural rubber coating；
(2) preparation method of corrosion-resistant super hydrophobic coating provided by the present invention passes through using through silane coupler modified
The multiple dimensioned coarse knot on super-hydrophobic coating material surface is moulded in hydrophobic nano-silica colloidal sol and nano-titanium dioxide collaboration
Structure substantially increases the hydrophobicity on coating material surface, and since nano-titanium dioxide surface hydroxyl is more, hydrophily is stronger.And
This disadvantage then can be just overcome through silane coupler modified hydrophobic nano-silica colloidal sol, moreover it is possible to it is super thin to increase it
Water stability further increases its self-cleaning ability, further, since titanium dioxide nature is stablized, corrosion resistance is strong, with warp
Silane coupler modified hydrophobic nano-silica synergistic effect, can enhance the corrosion resistance of super-hydrophobic coat.
(3) the preparation method condition of corrosion-resistant super hydrophobic coating provided by the present invention is simple, and technique is controllable, required equipment
It is common device, used raw material is easy to get and cheap, high production efficiency, is suitble to scale industrial production, and be made
Coating and a variety of substrates between adhesive force with higher, the excellent combination property of the coating coated, application prospect is wide
Wealthy, theoretical and practical significance is great.
Specific embodiment
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but the present invention is not
It is limited only to the following examples.
Embodiment 1-9
A kind of corrosion-resistant super hydrophobic coating and its preparation method and application, specific steps include:
It S1, is in mass ratio 0.8-1.2 parts: 0.01-0.15 part by SBS resin, natural rubber and solvent, 15-25 parts
Ratio is dissolved in solvent, and obtained SBS resin/natural rubber solution is stirred at room temperature；
Specifically, the solvent is one of toluene, dimethylbenzene, ethyl acetate, butyl acetate, tetrahydrofuran or more
Kind；
S2, by silane coupler modified nano silicon dioxide sol, (referred to as: modified manometer silicon dioxide is molten in proportion
Glue) and nano-titanium dioxide be added in step S1 in SBS resin/natural rubber solution obtained, be stirred at room temperature to obtain the final product；
Specifically, 1.0-2.0 parts of silane coupler modified nano silicon dioxide sol, nano-titanium dioxide 2.0-8.0
Part；
Specifically, silicon dioxide gel is the silane coupler modified nanometer of solid content 16-35% and partial size 20-55nm
Silicon dioxide gel, the partial size of the nano-titanium dioxide are 20-75nm；
1-9 of the embodiment of the present invention compared preparing using different test raw materials, using different technical parameters corrosion-resistant super
The test of hydrophobic coating, each specific experimental condition of embodiment are as shown in table 1 below.
The table of comparisons of test raw material employed in 1 embodiment of the present invention of table
Meanwhile coating made from the various embodiments described above being coated on different substrate, and test its performance.
Referring to standard GB/T/T 9286-1998 " frame of paint and varnish paint film is tested ", tested using cross-hatching
Super-hydrophobic coating material is stated in glass plate, polycarbonate plate, polymethyl methacrylate plate, polyvinyl chloride panel, surface of aluminum plate
Adhesive force；Referring to standard GB/T/T 6739-2006 " paint and varnish pencil method measures hardness of paint film ", testing coating material
Pencil hardness；It is old under 130 DEG C of high temperature to test contact angle (initial contact angle), coating material of the water droplet on coating material surface
Contact angle (the salt of contact angle (contact angle after aging) and coating after salt water immersion (3.5%NaCl) 10 days after changing 30 days
Contact angle after water impregnates), test data result is as shown in table 2 below.
The performance test results of prepared coating in 2 embodiment of the present invention of table
It can be seen from the results in table 2 corrosion-resistant super-hydrophobic coating and polycarbonate plate, polymethyl methacrylate
There is best adhesive force between plate, polyvinyl chloride panel, and the adhesive force between glass plate and aluminium sheet is slightly worse.This may be because
Can be partly dissolved or be swollen substrate for the solvent of super hydrophobic coating, cause SBS resin/natural rubber can with substrate molecule it
Between wind mutually, to improve the adhesive force between coating and substrate.From the point of view of the pencil hardness of coating surface, meet coating
General operational requirement.The ageing-resistant performance of corrosion-resistant super-hydrophobic coating is all very good, under 130 DEG C of high temperature after aging 30 days all still
With super-hydrophobicity.But the corrosion resistance difference of super-hydrophobic coat is larger, in addition to the coating of embodiment 1 and embodiment 2 is through salt
Water impregnates (3.5%NaCl) and still keeps outside super-hydrophobicity after 10 days, and the coating of other embodiments all loses original super-hydrophobicity.
Embodiment 1 is best.The effect of embodiment 1 it is optimal speculate the reason is that, the total additive amount of nanoparticle is suitable, furthermore what is used receives
The ratio of rice silica and nano-titanium dioxide is proper, the nano silica and nanometer two of appropriate amount and proper ratio
Titanium oxide modified synergic SBS resin/natural rubber has optimal effect.
It is in comparative analysis table 2 results, it can be seen that coating obtained by preparation method provided by the embodiment of the present invention
The hydrophobic performance of material is excellent, and performance is stablized, while having both good high temperature resistance, ageing-resistant performance and mechanical performance,
Comprehensive performance is substantially better than SBS resin and natural rubber coating, using through silane coupler modified hydrophobic nano titanium dioxide
The multiple dimensioned coarse structure on super-hydrophobic coating material surface is moulded in silica solution and nano-titanium dioxide collaboration, substantially increases coating
The adhesion property of material has good in a variety of substrate surfaces such as polycarbonate plate, polymethyl methacrylate plate, polyvinyl chloride panels
Good adhesive force, preferable hardness and excellent hydrophobic performance (150 ° of contact angle >) meets practical requirement, and 130
Under DEG C hot environment after aging 30 days, coating material still has super-hydrophobicity；Preferably, corrosion-resistant super-hydrophobic coating is through salt water
Super-hydrophobicity can still be kept after 10 days by impregnating (3.5%NaCl).Therefore, corrosion-resistant super-hydrophobic coating material of the present invention
With good corrosion-resistant, high temperature resistant and ageing-resistant performance, long service life；Meanwhile the corrosion-resistant super hydrophobic coating is suitable for
Industrial mass production has the powerful market competitiveness；Preparation method condition is simple, and technique is controllable, and required equipment is
Common device, used raw material is easy to get and cheap, high production efficiency, is suitble to scale industrial production, and painting obtained
Material is suitable for a variety of substrates, and the excellent combination property of the coating coated has a extensive future, theoretical and practical significance weight
Greatly.
The above is only a preferred embodiment of the present invention, it is noted that come for those of ordinary skill in the art
It says, without departing from the concept of the premise of the invention, several modifications and variations can also be made, these belong to of the invention
Protection scope.
Claims (8)
1. a kind of corrosion-resistant super hydrophobic coating, which is characterized in that the raw material including following parts by weight:
0.8-1.2 parts of SBS resin, 0.01-0.15 parts of natural rubber, 10-30 parts of solvent, silane coupler modified nano-silica
0.1-2.0 parts of SiClx colloidal sol, 2.0-8.0 parts of nano-titanium dioxide；
Wherein, the partial size of the improved silica in the silane coupler modified silicon dioxide gel is 10-150 nm；It is described
The partial size of nano-titanium dioxide is 10-200 nm.
2. corrosion-resistant super hydrophobic coating according to claim 1, which is characterized in that the silane coupler modified nanometer
The solvent of silicon dioxide gel is one of toluene, dimethylbenzene and methyl ethyl ketone, and colloidal sol solid content is 5-30 %.
3. a kind of corrosion-resistant super hydrophobic coating, which is characterized in that the raw material including following parts by weight:
0.8-1.2 parts of SBS resin, 0.01-0.15 parts of natural rubber, 15-25 parts of solvent, silane coupler modified nano-silica
1.0-2.0 parts of SiClx colloidal sol, 2.0-8.0 parts of nano-titanium dioxide；
Wherein, the partial size of the improved silica in the silane coupler modified silicon dioxide gel is 20-55 nm, admittedly contain
Measure 16-35 %；The partial size of the nano-titanium dioxide is 25-75 nm.
4. corrosion-resistant super hydrophobic coating according to claim 1 or 3, which is characterized in that the solvent is toluene, diformazan
One of benzene, ethyl acetate, butyl acetate, tetrahydrofuran are a variety of.
5. corrosion-resistant super hydrophobic coating according to claim 1 or 3, which is characterized in that described silane coupler modified
Silicon dioxide gel the preparation method is as follows: using ethyl orthosilicate as silicon source, ammonium hydroxide is catalyst, synthesizes and receives in METHANOL MEDIUM
Rice silicon dioxide gel；Then surface is carried out to nano silica using silane coupling agent to be modified, obtain silane coupling agent and change
The silicon dioxide gel of property.
6. a kind of preparation method of corrosion-resistant super hydrophobic coating as claimed in claim 1 or 3 characterized by comprising
S1, by the raw material parts in claim 1, SBS resin, natural rubber are mixed according to the ratio with solvent, stirred at room temperature
Mixing obtains SBS resin/natural rubber solution；
S2, by the raw material parts in claim 1, by silane coupler modified nano silicon dioxide sol and nanometer titanium dioxide
Titanium is added in step S1 in SBS resin/natural rubber solution obtained, is stirred at room temperature to get to corrosion-resistant super-hydrophobic
Coating.
7. preparation method according to claim 6, which is characterized in that in step S2, the mixing time is 30-120
min。
8. a kind of corrosion-resistant super-hydrophobic coating material, which is characterized in that it is made of coating described in claim 1 or 3, it is described
The contact angle of coating is greater than 150°, roll angle is less than 6°。
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111254700A (en) * | 2020-01-19 | 2020-06-09 | 荆门市诺维英新材料科技有限公司 | Textile modified material and preparation method thereof |
| CN111393118A (en) * | 2020-03-23 | 2020-07-10 | 普定县百安新型环保建筑材料有限责任公司 | Novel barium slag and fly ash hollow building block and preparation method thereof |
| CN112961547A (en) * | 2021-02-01 | 2021-06-15 | 山西吸睛科技有限公司 | Recyclable film protecting agent and preparation method and application thereof |
| CN113122036A (en) * | 2021-03-18 | 2021-07-16 | 华帝股份有限公司 | Hydrophobic coating, preparation method and workpiece surface treatment method |
| CN114836110A (en) * | 2022-04-30 | 2022-08-02 | 江苏国强镀锌实业有限公司 | Nano modified hot-dip galvanized polyester coating and preparation method thereof |
| CN115637073A (en) * | 2022-11-08 | 2023-01-24 | 河南兴安新型建筑材料有限公司 | Nano-coated aerated concrete reinforcement preservative and preparation method thereof |
| CN116218321A (en) * | 2023-03-24 | 2023-06-06 | 华南理工大学 | Bi-component waterborne epoxy anticorrosive paint and preparation method and application thereof |
| CN116446216A (en) * | 2023-02-20 | 2023-07-18 | 浙江画之都文化创意有限公司 | Cloud dragon paper high-strength transparent super-hydrophobic coating and low-cost macro construction method thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111254700A (en) * | 2020-01-19 | 2020-06-09 | 荆门市诺维英新材料科技有限公司 | Textile modified material and preparation method thereof |
| CN111393118A (en) * | 2020-03-23 | 2020-07-10 | 普定县百安新型环保建筑材料有限责任公司 | Novel barium slag and fly ash hollow building block and preparation method thereof |
| CN112961547A (en) * | 2021-02-01 | 2021-06-15 | 山西吸睛科技有限公司 | Recyclable film protecting agent and preparation method and application thereof |
| CN113122036A (en) * | 2021-03-18 | 2021-07-16 | 华帝股份有限公司 | Hydrophobic coating, preparation method and workpiece surface treatment method |
| CN114836110A (en) * | 2022-04-30 | 2022-08-02 | 江苏国强镀锌实业有限公司 | Nano modified hot-dip galvanized polyester coating and preparation method thereof |
| CN115637073A (en) * | 2022-11-08 | 2023-01-24 | 河南兴安新型建筑材料有限公司 | Nano-coated aerated concrete reinforcement preservative and preparation method thereof |
| CN116446216A (en) * | 2023-02-20 | 2023-07-18 | 浙江画之都文化创意有限公司 | Cloud dragon paper high-strength transparent super-hydrophobic coating and low-cost macro construction method thereof |
| CN116218321A (en) * | 2023-03-24 | 2023-06-06 | 华南理工大学 | Bi-component waterborne epoxy anticorrosive paint and preparation method and application thereof |
| CN116218321B (en) * | 2023-03-24 | 2024-04-02 | 华南理工大学 | Bi-component waterborne epoxy anticorrosive paint and preparation method and application thereof |
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