CN110373087A - A kind of aqueous photoresponse self-repairing coating material and preparation method thereof - Google Patents
A kind of aqueous photoresponse self-repairing coating material and preparation method thereof Download PDFInfo
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- CN110373087A CN110373087A CN201910604395.9A CN201910604395A CN110373087A CN 110373087 A CN110373087 A CN 110373087A CN 201910604395 A CN201910604395 A CN 201910604395A CN 110373087 A CN110373087 A CN 110373087A
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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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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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
- C09D7/20—Diluents or solvents
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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
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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
Abstract
The invention discloses a kind of aqueous photoresponse self-repairing coating material and preparation method thereof, the coating material is mixed by organic silicon modified aqueous epoxy resin latex, MXene, water, aqueous amine curing agent, dispersing agent, levelling agent and defoaming agent by certain mass number；The present invention is using two-dimensional layer material MXene as photo-thermal filler, MXene and organic silicon modified aqueous epoxy resin is soluble in water, then aqueous amine curing agent is added and aqueous photoresponse self-repairing coating material can be obtained in auxiliary agent, it solves the agglomeration traits of MXene simultaneously, improves the photo-thermal efficiency of MXene；The coating material preparation process is simple, safety and environmental protection, and the controllable quick selfreparing of response progress can be irradiated by visible or infrared light after being prepared into coating, is suitble to large-scale production.
Description
Technical field
The invention belongs to selfreparing polymeric coating material technical fields, certainly more particularly, to a kind of aqueous photoresponse
Reparation material and preparation method thereof.
Background technique
In recent years, polymer coating materials have many advantages, such as that intensity height, good toughness, light weight, processing performance are excellent, thus
It is widely used in ship, building, the corrosion multiple fields such as anti-corrosion and military project.However, using in polymer coating materials
Cheng Zhong, coating material surface and inside are easy to produce scratch and crackle, such as repair not in time, the mechanical property of polymer coating must
Can so it decline, so as to shorten the service life of material, it is often more important that, there may be huge security risks for damaged material.
In view of the above-mentioned problems, researcher proposes that self-repair technology, i.e. object are able to carry out self-regeneration when impaired, restore original category
Property, thus a new technique for keeping itself fully functional.
The main repair mechanism of coatings can be divided into from two class of principal mode and non-autonomous type, wherein being divided into film forming from principal mode
Substance type and inhibition dosage form, and non-autonomous type is then divided into temperature-responsive and photoresponse stimulation etc..For self-healing polymers, in addition to
Partial self-repair procedure is complete spontaneous progress, and most polymers need environmental stimuli, such as light, heat, humidity to touch
Send out its self-repair procedure.Be concentrated mainly on hot initiation about the research of selfreparing at present, but heat cause can only short distance cause from
It repairs, and the heating process of heat initiation self-repair method can make the structure at damage of material position and surrounding polymer material
It is destroyed, light triggering selfreparing has the characteristics that controllably quick, thus obtains extensive use in selfreparing field.Light triggering
The bright characteristics of selfreparing are mainly reflected in following 3 aspects: (1) since light be able to carry out long-distance communications, Ke Yili
With light Remote triggering self-repair procedure；(2) propagation of light is spatially controllable, and the fixed point that polymer may be implemented is reviewed one's lessons by oneself
It is multiple；(3) by stopping illumination or starting illumination, light, which triggers self-repair procedure, to be stopped or be started with moment.In Macroscopic single crystal
The nanoparticle that can cause photo-thermal effect is introduced in the process as photo-thermal filler, such as gold nanoparticle, poly-dopamine nanoparticle
Son becomes a kind of novel coatings application.But since gold nanoparticle is sufficiently expensive, the light of excitation selfreparing needs
The problems such as intensity is high, and the synthesis of poly-dopamine nanoparticle is sufficiently complex, so that these applications are difficult to realize.
MXene be the transition metal carbide with two-dimensional layered structure similar with graphene found in recent years or
Nitride, nearly 70 kinds of presently found MXene, including Ti3C2Tx, Ti2CTx, V2CTx, Nb2CTx, Nb4C3Tx,
Ta4C3Tx, Ti4N3Tx.The high advantage of the conductive good, large specific surface area of MXene, intensity, energy storage, electronics, composite material,
The fields such as solar battery, anticorrosion coating material are with a wide range of applications.
Patent 201810619992.4 discloses a kind of modified anticorrosion coating material of novel MXenes and preparation method thereof, institute
The anticorrosion coating material stated is that be that filler mixes by stirring using resin as matrix, MXenes obtained, and MXenes nano material exists
Corrosive medium is obstructed as a kind of excellent barrier in resin matrix, creates more anfractuose path, Lai Yanhuan corrosivity
The diffusion of medium, to protect metallic matrix；The relationship of any MXenes filler and self-repairing coating material is not disclosed.
Currently, about MXene in photoresponse self-repairing coating material application have not been reported, moreover, MXene compared with
Bigger serface is easy dispersion in water, therefore how MXene to be added in matrix without reuniting, and compel to be essential at present
It to be solved, while current coatings resin is mostly solvent type, there are toxic solvent, volatile, waste, pollution environment
The disadvantages of, do not meet environmental requirement.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the defect of the prior art and deficiency, provide a kind of aqueous photoresponse from
Reparation material, while solving that MXene surface area is big, being easy to reunite in coating material causes photo-thermal efficiency is bad to ask
Topic, and safety and environmental protection.
A second object of the present invention is to provide the preparation methods of above-mentioned aqueous photoresponse self-repairing coating material.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
Current research discovery, MXene have good photoproduction thermal effect, and photo-thermal under visible-near-infrared irradiation
Conversion ratio is up to 85%, can be used for preparing photoresponse coatings.
Therefore application of the present invention protection MXene first in preparation photoresponse reparation material.
A kind of aqueous photoresponse self-repairing coating material is prepared: organic by each component mixing of following mass fraction
100~200 parts of silicon modified aqueous epoxy emulsion, 12~16 parts of MXene, 20~40 parts of water, aqueous amine curing agent 30~60
Part, 1~2 part of dispersing agent, 1~2 part and 1~2 part of defoaming agent of levelling agent.
MXene is a kind of transition metal carbide or nitridation with two-dimensional layered structure similar with graphene-structured
Object, the study found that MXene has good photoproduction thermal effect under visible-near-infrared irradiation, and solar-thermal conversion rate is up to
85%, after inventor is the study found that MXene is mixed as photo-thermal filler and coated substrate, obtained coating has good
Photoresponse self-repair function can carry out selfreparing under low intensity visible light or near infrared light, have controllable quick
Feature.Coating material of the present invention takes water as a solvent using MXene as photo-thermal filler, while organic silicon modified aqueous ring is added
Oxygen lotion also solves the dispersion of MXene in the base, improves the photo-thermal efficiency of MXene, improves coating selfreparing
Effect, and then realize the long-effective protection to substrate.Coating material of the present invention takes water as a solvent, and is free of any organic solvent,
And non-volatility organic matter generates, safety and environmental protection.
Preferably, the aqueous photoresponse self-repairing coating material by following mass fraction each component mix preparation and
At: 40~60 parts of organic silicon modified aqueous epoxy emulsion, 3~5 parts of MXene, 10~15 parts of water, aqueous amine curing agent 10~
20 parts.
Preferably, the aqueous photoresponse self-repairing coating material by following mass fraction each component mix preparation and
At: 40~60 parts of organic silicon modified aqueous epoxy emulsion, 3~5 parts of MXene, 10~15 parts of water, aqueous amine curing agent 10~
20 parts.
Specifically, the MXene is single layer Ti3C2Mxene。
Preferably, the single layer Ti3C2MXene passes through multilayer Ti3C2MXene and DMSO mixing, ultrasound, mistake
It is obtained after filter, drying.
Specifically, the single layer Ti3C2MXene passes through 5~10g multilayer Ti3C2MXene is mixed with 60~100mLDMSO and is stirred
Mix 12~for 24 hours, 1~2h of ultrasound under the conditions of 300~500W, filtering, drying obtain.
Preferably, the multilayer Ti3C2MXene is by by MAX phase material Ti3AlC2It is mixed, adjusts molten with 50%HF
Liquid pH to 5~7, filtering, after obtained solid is dried to obtain the final product.
Preferably, the organic silicon modified aqueous epoxy resin solid content is 45%~55%.
Preferably, the organic silicon modified aqueous epoxy resin passes through aminopropyl triethoxysilane (KH550), dimethyl
Diethoxy silane and aqueous epoxy resins (F0707) are uniformly mixed.
Preferably, the organic silicon modified aqueous epoxy resin is prepared by each component mixing of following mass fraction:
15~20 parts of aminopropyl triethoxysilane, 20~40 parts of dimethyl diethoxysilane, 100~120 parts of aqueous epoxy resins.
Preferably, the mixing reaction time is 2~5h, by aminopropyl triethoxysilane, dimethyl diethoxy
Silane and aqueous epoxy resins are uniformly mixed.
It is highly preferred that the reaction time is 3h.
Preferably, the aqueous amine curing agent is Ai Dike EA-15.
Preferably, the dispersing agent is PE100.
Preferably, the levelling agent is BYK346.
Preferably, the defoaming agent is BYK-028.
The preparation method of above-mentioned aqueous photoresponse self-repairing coating material is also claimed in the present invention, and 100~200 parts are had
The silicon modified aqueous epoxy resin latex of machine, 12~16 parts of MXene are dissolved in 20~40 parts of water, and 1500~2000rpm stirring 0.5~
1h, be then added 30~60 parts of aqueous amine curing agent, 1~2 part of dispersing agent, 1~2 part of levelling agent and 1~2 part of defoaming agent in
1500~2500rpm stirring to get.
By above-mentioned organic silicon modified aqueous epoxy emulsion and single layer Ti3C2After MXene is soluble in water, single layer can be made
Ti3C2MXene is evenly spread in organic silicon modified aqueous epoxy emulsion, and aqueous amine curing agent and auxiliary agent is then added
Aqueous photoresponse self-repairing coating material is prepared, after which is made coating, as selfreparing works well
Aqueous photoresponse coatings.
Preferably, the mixing time is 1~2h, to be uniformly mixed raw material by suitably stirring.
The coating that the aqueous photoresponse self-repairing coating material is prepared can be by ringing visible light and infrared light
Controllable quick selfreparing should be carried out, and scratch can quickly be repaired under low laser optical intensity density, and then is realized to substrate
Long-effective protection；In addition, coating material of the present invention takes water as a solvent, other organic solvents are not contained, non-volatility is organic
Object, safety and environmental protection, and the preparation process is simple, can be completed at room temperature.
Compared with prior art, the invention has the following advantages:
The present invention provides a kind of photoresponse self-repairing coating material, by adding photo-thermal filler in water-base resin
MXene, the coating can carry out selfreparing under low intensity visible light or near infrared light, have controllable quickly special
Point.Organic silicon modified aqueous epoxy emulsion is added by taking water as a solvent using MXene as photo-thermal filler in coating material, also
It solves the dispersion of MXene in the base, improves the photo-thermal efficiency of MXene, improve the effect of coating selfreparing, in turn
Realize the long-effective protection to substrate.Coating material of the present invention takes water as a solvent, and is free of any organic solvent, and non-volatility
Organic matter generates, safety and environmental protection, and all techniques are completed at room temperature, energy conservation and environmental protection, is suitble to large-scale production.
Specific embodiment
Further illustrate the present invention below in conjunction with specific embodiment, but embodiment the present invention is not done it is any type of
It limits.Unless stated otherwise, the present invention uses reagent, method and apparatus is the art conventional reagents, method and apparatus.
Unless stated otherwise, following embodiment agents useful for same and material are commercially available.
A kind of preparation method of aqueous photoresponse self-repairing coating material of embodiment 1
One, method
(1) preparation of organic silicon modified aqueous epoxy emulsion
By 15g aminopropyl triethoxysilane (KH550), 30g dimethyl diethoxysilane and 100g water-base epoxy tree
Rouge (F0707) mixes, and stirs 3h under 1500rpm, obtains organic silicon modified aqueous epoxy resin.
(2) single layer Ti3C2The preparation of MXene
By 10g MAX phase material Ti3AlC2It is added to stirring 18h in 100mL 50%HF to perform etching, then solution filters
Being washed to pH value is 6, and filtrate filtering obtained solid drying can be obtained multilayer Ti3C2MXene, by 10g Ti3C2MXene with
100mL DMSO is mixed 18h and carries out intercalation, and ultrasound 1h, acquired solution filtering drying can obtain single layer under the conditions of 500w
Ti3C2MXene。
(3) preparation of photoresponse self-repairing coating material
By the organic silicon modified aqueous epoxy emulsion of 100g, 8g Ti3C2MXene and 20g water stirs 1h under 1500rpm, then
30g aqueous amine curing agent EA-15 (Ai Dike), 1g dispersing agent PE100,1g levelling agent BYK346 and 1g defoaming agent is added
BYK028 stirs 2h at 2500rpm to get photoresponse self-repairing coating material.
Ti in the photoresponse self-repairing coating material being prepared3C2MXene is uniformly dispersed.
Coating selfreparing test: with standardized road width on sharp blade coating after fully cured less than 100 μm
Scratch, with 473nm visible light lasers, optical intensity density 2.5Wcm-2Irradiation 2min can carry out the scratch of coating surface
It repairs.
A kind of preparation method of aqueous photoresponse self-repairing coating material of embodiment 2
One, method
(1) preparation of organic silicon modified aqueous epoxy emulsion
By 20g aminopropyl triethoxysilane (KH550), 30g dimethyl diethoxysilane and 110g water-base epoxy tree
Rouge (F0707) mixes, and stirs 3h under 1500rpm, obtains organic silicon modified aqueous epoxy resin.
(2) single layer Ti3C2The preparation of MXene
By 10g MAX phase material Ti3AlC2It is added to stirring 18h in 100mL 50%HF to perform etching, then solution filters
Being washed to pH value is 5, and filtrate filtering obtained solid drying can be obtained multilayer Ti3C2MXene, by 10g Ti3C2MXene with
80mL DMSO mixing carries out intercalation for 24 hours, and ultrasound 2h, acquired solution filtering drying can obtain single layer under the conditions of 300w
Ti3C2MXene。
(3) preparation of photoresponse self-repairing coating material
By the organic silicon modified aqueous epoxy emulsion of 80g, 6g Ti3C2MXene and 10g water stirs 0.5h under 1500rpm,
Add 20g aqueous amine curing agent EA-15 (Ai Dike), 0.5g dispersing agent PE100,0.5g levelling agent BYK346 and 0.5g disappear
Infusion BYK028 stirs 2h at 2000rpm to get photoresponse self-repairing coating material.
Ti in the photoresponse self-repairing coating material being prepared3C2MXene is uniformly dispersed.
Coating selfreparing test: with standardized road width on sharp blade coating after fully cured less than 100 μm
Scratch, with 473nm visible light lasers, optical intensity density 1.5Wcm-2Irradiation 5min can carry out the scratch of coating surface
It repairs.
A kind of preparation method of aqueous photoresponse self-repairing coating material of embodiment 3
One, method
(1) preparation of organic silicon modified aqueous epoxy emulsion
By 15g aminopropyl triethoxysilane (KH550), 30g dimethyl diethoxysilane and 120g water-base epoxy tree
Rouge (F0707) mixes, and stirs 3h under 1500rpm, obtains organic silicon modified aqueous epoxy resin.
(2) single layer Ti3C2The preparation of MXene
By 10g MAX phase material Ti3AlC2It is added to stirring 18h in 100mL 50%HF to perform etching, then solution filters
Being washed to pH value is 7, and filtrate filtering obtained solid drying can be obtained multilayer Ti3C2MXene, by 5g Ti3C2MXene and 60mL
DMSO is mixed 12h and carries out intercalation, and ultrasound 2h, acquired solution filtering drying can obtain single layer under the conditions of 400w
Ti3C2MXene。
(3) preparation of photoresponse self-repairing coating material
By the organic silicon modified aqueous epoxy emulsion of 50g, 6g Ti3C2MXene and 15g water stirs 1h under 2000rpm, then
15g aqueous amine curing agent EA-15 (Ai Dike), 0.5g dispersing agent PE100,0.5g levelling agent BYK346 and 0.5g defoaming is added
Agent BYK028 stirs 2h at 1500 rpm to get photoresponse self-repairing coating material.
Ti in the photoresponse self-repairing coating material being prepared3C2MXene is uniformly dispersed.
Coating selfreparing test: with standardized road width on sharp blade coating after fully cured less than 100 μm
Scratch, with 785nm near infrared light laser, optical intensity density 2.0Wcm-2Irradiate 5min can scratch to coating surface into
Row is repaired.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
- Application of the 1.MXene in preparation photoresponse reparation material.
- 2. a kind of aqueous photoresponse self-repairing coating material, which is characterized in that mix preparation by each component of following mass fraction It forms: 100~200 parts of organic silicon modified aqueous epoxy resin latex, 12~16 parts of MXene, 20~40 parts of water, aqueous amine 30~60 parts of curing agent, 1~2 part of dispersing agent, 1~2 part and 1~2 part of defoaming agent of levelling agent.
- 3. aqueous photoresponse self-repairing coating material according to claim 2, which is characterized in that the MXene is single layer Ti3C2Mxene。
- 4. aqueous photoresponse self-repairing coating material according to claim 3, which is characterized in that the single layer Ti3C2MXene passes through multilayer Ti3C2MXene and DMSO is mixed, ultrasound, filters, obtains after drying.
- 5. aqueous photoresponse self-repairing coating material according to claim 4, which is characterized in that, the single layer Ti3C2MXene passes through 5~10g multilayer Ti3C2MXene and 60~100mL DMSO mixing 12~for 24 hours, in 300~500W Under the conditions of 1~2h of ultrasound, filtering, drying obtain.
- 6. aqueous photoresponse self-repairing coating material according to claim 4 or 5, which is characterized in that the multilayer Ti3C2MXene is by by MAX phase material Ti3AlC2It is mixed with 50%HF, adjusts pH value of solution to 5~7, filter, by gained After solid drying to obtain the final product.
- 7. aqueous photoresponse self-repairing coating material according to claim 2, which is characterized in that organic silicon modified aqueous asphalt mixtures modified by epoxy resin Rouge solid content is 45%~55%.
- 8. aqueous photoresponse self-repairing coating material according to claim 2 or 4, which is characterized in that the organosilicon changes Property aqueous epoxy resins uniformly mixed by aminopropyl triethoxysilane, dimethyl diethoxysilane and aqueous epoxy resins It forms.
- 9. aqueous photoresponse self-repairing coating material according to claim 5, which is characterized in that the organic-silicon-modified water Property epoxy resin by following mass fraction each component mixing be prepared: 15~20 parts of aminopropyl triethoxysilane, diformazan 20~40 parts of base diethoxy silane, 100~120 parts of aqueous epoxy resins.
- 10. the preparation method of any one of the claim 1~9 aqueous photoresponse self-repairing coating material, which is characterized in that will 100~200 parts of organic silicon modified aqueous epoxy resin latexes, 12~16 parts of MXene are dissolved in 20~40 parts of water, 1500~ 2000rpm stir 0.5~1h, then be added 30~60 parts of aqueous amine curing agent, 1~2 part of dispersing agent, 1~2 part of levelling agent and 1~2 part of defoaming agent in 1500~2500rpm stir to get.
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Cited By (6)
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| CN111138952A (en) * | 2020-01-22 | 2020-05-12 | 江苏金陵特种涂料有限公司 | Preparation method of water-based self-repairing coating material |
| CN111303770A (en) * | 2020-02-27 | 2020-06-19 | 浙江寰洲高分子材料科技有限公司 | Bio-based water-based anticorrosive conductive coating for bridge building protection and health monitoring and preparation method thereof |
| CN112920638A (en) * | 2021-01-25 | 2021-06-08 | 西北工业大学 | MXene-based aqueous nano electrothermal composite coating and preparation method thereof |
| CN113004776A (en) * | 2021-02-03 | 2021-06-22 | 中山大学 | Water-based self-repairing coating and application thereof |
| CN114907755A (en) * | 2022-04-02 | 2022-08-16 | 山东力合新材料科技有限公司 | Preparation method of visible light induced self-repairing coating based on two-dimensional titanium carbide |
| CN116200091A (en) * | 2023-02-18 | 2023-06-02 | 辽宁大学 | High-compactness multi-scale aqueous epoxy corrosion-resistant coating and preparation method and application thereof |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111138952A (en) * | 2020-01-22 | 2020-05-12 | 江苏金陵特种涂料有限公司 | Preparation method of water-based self-repairing coating material |
| CN111303770A (en) * | 2020-02-27 | 2020-06-19 | 浙江寰洲高分子材料科技有限公司 | Bio-based water-based anticorrosive conductive coating for bridge building protection and health monitoring and preparation method thereof |
| CN112920638A (en) * | 2021-01-25 | 2021-06-08 | 西北工业大学 | MXene-based aqueous nano electrothermal composite coating and preparation method thereof |
| CN113004776A (en) * | 2021-02-03 | 2021-06-22 | 中山大学 | Water-based self-repairing coating and application thereof |
| CN114907755A (en) * | 2022-04-02 | 2022-08-16 | 山东力合新材料科技有限公司 | Preparation method of visible light induced self-repairing coating based on two-dimensional titanium carbide |
| CN114907755B (en) * | 2022-04-02 | 2023-09-19 | 山东力合新材料科技有限公司 | Preparation method of visible light-induced self-repairing coating based on two-dimensional titanium carbide |
| CN116200091A (en) * | 2023-02-18 | 2023-06-02 | 辽宁大学 | High-compactness multi-scale aqueous epoxy corrosion-resistant coating and preparation method and application thereof |
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Application publication date: 20191025 |