CN105585939A - Self-repairing coating with rust conversion function and preparation method thereof - Google Patents
Self-repairing coating with rust conversion function and preparation method thereof Download PDFInfo
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- CN105585939A CN105585939A CN201610154870.3A CN201610154870A CN105585939A CN 105585939 A CN105585939 A CN 105585939A CN 201610154870 A CN201610154870 A CN 201610154870A CN 105585939 A CN105585939 A CN 105585939A
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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
- 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
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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
- C09D7/63—Additives non-macromolecular organic
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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
- C09D7/65—Additives macromolecular
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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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- 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
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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- 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
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four 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)
- Inorganic Chemistry (AREA)
- Paints Or Removers (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Details Of Rigid Or Semi-Rigid Containers (AREA)
Abstract
The invention designs a self-repairing coating with a rust conversion function and a preparation method thereof and belongs to the field of metal anti-corrosion coatings. The self-repairing coating with the rust conversion function is characterized in that nanometer containers where a rust conversion agent and a corrosion inhibitor are encapsulated are dispersed into epoxy resin, the rust conversion agent in the coating can convert loose rust before film forming of the corrosion inhibitor, the corrosion inhibitor released by the self-repairing coating directly generates a compact protective film on the surface of carbon steel, and therefore the protective effect of the self-repairing coating is greatly enhanced. The self-repairing coating with the rust conversion function is characterized in that the nanometer containers where the rust conversion agent is encapsulated and the nanometer containers where the corrosion inhibitor is encapsulated are dispersed into epoxy resin, the epoxy resin is mixed with a certain amount of epoxy resin curing agent, a dispersing agent, a diluting agent and a defoaming agent, the coating is prepared, and the surface of carbon steel is coated with the coating so that the self-repairing coating with the rust conversion function can be formed.
Description
Technical field
The present invention relates to a kind of coatings with iron rust transformation function and preparation method thereof, belong to anti-corrosive metal coating field.
Background technology
Organic anti-corrosive coating is that organic coating and functional filler are coated in to the protective film that metal surface forms by certain method. Coating, in long-term use procedure, can suffer wearing and tearing, abrasion and abrasion, the phenomenons such as bubbling, pin hole and micro-crack easily occurs, thereby make the metal exposed of small size in corrosive medium, causes local corrosion, causes coating to lose efficacy in advance. In recent years; people are for the research increasing year by year of Smart self-repairing corrosion-inhibiting coating, and when this type coating breaks, the functional microsphere or the nano container that are dispersed in coating can discharge consolidant or corrosion inhibiter; generate diaphragm in metal surface, stop or slow down corrosion of metal process. Coatings becomes and improves the one novelty of coating antiseptic effect and effective method. White etc. utilize the opening of bicyclopentadiene and Grubbs catalyst to repair damaged macromolecular material. After this, self-repair technology is applied to corrosion-inhibiting coating field by researchers, and obtained development rapidly.
At present, about the research of selfreparing corrosion-inhibiting coating roughly can be divided into two classes: a class is to utilize polymer microsphere or nano container encapsulation polymerizer, polymerizer is if bicyclopentadiene, epoxy resin, isocyanates, linseed wet goods are under the effect of catalyst or curing agent, be hydrolyzed, the reaction generation high molecular polymer such as crosslinked and polymerization crams the micro-crack place in coating, isolation Korrosionsmedium and metal, play corrosion-resistant effect; Another kind of is utilize polymer microsphere or nano container encapsulation corrosion inhibiter and be distributed in coating. The electron-donating group such as N, S, O in inhibitor molecular and metal form co-ordinate covalent bond and produce chemisorbed; Charged corrosion inhibiter group produces physical absorption with the metal with opposite charges; The acting in conjunction of physical absorption and chemisorbed makes micro-inhibitor molecular cover metal surface, the metallic matrix that protective finish micro-crack place contacts with corrosive medium.
Conventionally, the self-repair procedure of corrosion-inhibiting coating comprises following step: (1) coating produces micro-crack after breaking; (2) inhibitor molecular discharges from high molecular polymer microballoon or nano container; (3) inhibitor molecular migrates to metal surface; (4) inhibitor molecular forms diaphragm in metal surface. In actual applications, there is following problem urgently to be resolved hurrily: after coating is broken in corrosive environment, metal contacts with water, oxygen and chlorion and electrochemical corrosion occurs and reacts, the speed ratio above-mentioned steps (3) of this reaction and step (4) are fast, and this just causes corrosion inhibiter first to adsorb with corrosion product. The structure of carbon steel Initial Corrosion product in seawater is more loose, and it is not fine and close that corrosion inhibiter covers the diaphragm generating above, and protection effect can significantly reduce. Therefore, before corrosion inhibiter film forming, very important loose iron rust conversion, this corrosion inhibiter that can make coatings discharge directly generates fine and close diaphragm at steel surface, thereby greatly strengthens the protection effect of coatings.
Summary of the invention
The present invention proposes a kind of coatings with iron rust transformation function, by add the nano container of encapsulation converting agent of iron rust and corrosion inhibiter in coating, make coating have the function of iron rust conversion and selfreparing concurrently, another object of the present invention is to provide a kind of preparation method of the coatings with iron rust transformation function, the method preparation technology is simple, cost is low, safety and environmental protection.
For achieving the above object; the technical solution used in the present invention is: a kind of coatings with iron rust transformation function; the nano container of encapsulation converting agent of iron rust and corrosion inhibiter is distributed in epoxy resin; ensure, before corrosion inhibiter and metal generation diaphragm, iron rust to be converted into fine and close diaphragm.
A preparation method with the coatings of iron rust transformation function, comprises the following steps:
(1) adopt self-assembly method preparation layer by layer to encapsulate the nano container of converting agent of iron rust;
(2) adopt self-assembly method preparation layer by layer to encapsulate the nano container of corrosion inhibiter;
(3) nano container of the nano container of encapsulation converting agent of iron rust, encapsulation corrosion inhibiter is distributed in epoxy resin;
(4) above-mentioned epoxy resin and a certain amount of epoxy curing agent, dispersant, diluent, defoamer are mixed and made into coating;
(5) above-mentioned coating is coated in to steel surface and forms the coatings with iron rust transformation function.
As preferably, the preparation process of the nano container of described step (1) encapsulation converting agent of iron rust is:
Get the nanometer SiO that mass fraction is 5-10%2Dispersion liquid, mixes with polymine (PEI) solution of 2-10g/L, and uniform stirring, centrifugation, obtain SiO2/ PEI. Get SiO2/ PEI particle mixes with tannic acid (TA) solution of 0.1-10g/L, and uniform stirring, centrifugation, obtain SiO2/ PEI/TA; Repeat above-mentioned steps three times, obtain encapsulating the nano container of converting agent of iron rust tannic acid.
As preferably, the preparation process of the nano container of described step (2) encapsulation corrosion inhibiter is:
Get the nanometer SiO that mass fraction is 5-10%2Dispersion liquid, mixes with polymine (PEI) solution of 2-10g/L, and uniform stirring, centrifugation, obtain SiO2/ PEI. Get SiO2/ PEI particle mixes with corrosion inhibiter (INH) solution of 0.1-2g/L, and uniform stirring, centrifugation, obtain SiO2/ PEI/INH; Repeat above-mentioned steps three times, obtain encapsulating the nano container of corrosion inhibiter.
As preferably, the corrosion inhibiter in described step (2) adopts the mixture of several corrosion inhibiter such as BTA, oxine and poly-aspartate.
As preferably, the mass ratio of the nano container of the nano container of the encapsulation converting agent of iron rust in described step (3) and encapsulation corrosion inhibiter is 1:1.
As preferably, in described step (3), the encapsulation nano container of corrosion inhibiter and the mass ratio of epoxy resin are 1:10-20.
As preferably, in described step (4), the mass ratio of epoxy curing agent and epoxy resin is 1:2.
Beneficial effect of the present invention is:
The present invention has the coatings of iron rust transformation function; converting agent of iron rust in coating can transform loose iron rust before corrosion inhibiter film forming; the corrosion inhibiter that coatings is discharged directly generates fine and close diaphragm at steel surface, thereby greatly strengthens the protection effect of coatings.
The present invention has the preparation method of the coatings of iron rust transformation function, and manufacturing process is simple, and coating process is not used poisonous organic solvent, pollution-free.
The coatings that the present invention has an iron rust transformation function is adapted to the corrosion protection of the conventional carbon steel material of ocean engineering, for the exploitation of marine steel structure coating new technology provides guidance, has broad application prospects.
Brief description of the drawings
After the Q235 carbon steel electrode test piece cut of the coating coatings that Fig. 1 provides for the embodiment of the present invention 1 in simulated seawater the AC impedance spectrogram of 96 hours, as can be seen from the figure along with time lengthening, the impedance radius of coating increases gradually, has shown good self-healing properties.
Specific embodiment
Below in conjunction with Figure of description, the invention will be further described, and protection scope of the present invention is not only confined to following examples.
Embodiment 1
Get mass fraction and be 5% nanometer SiO2Dispersion liquid, mixes with polymine (PEI) solution of 5g/L, and uniform stirring, centrifugation, obtain SiO2/ PEI. Get SiO2/ PEI particle mixes with tannic acid (TA) solution of 1g/L, and uniform stirring, centrifugation, obtain SiO2/ PEI/TA; Repeat above-mentioned steps three times, obtain encapsulating the nano container of converting agent of iron rust tannic acid.
Get mass fraction and be 5% nanometer SiO2Dispersion liquid, mixes with polymine (PEI) solution of 5g/L, and uniform stirring, centrifugation, obtain SiO2/ PEI. Get SiO2/ PEI particle mixes with corrosion inhibiter (INH) solution of 1g/L, and uniform stirring, centrifugation, obtain SiO2/ PEI/INH; Repeat above-mentioned steps three times, obtain encapsulating the nano container of corrosion inhibiter.
Get the nano container 1g of above-mentioned encapsulation converting agent of iron rust, the nano container 1g of encapsulation corrosion inhibiter, epoxy resin 10g, is distributed in epoxy resin; Add again 5g epoxy curing agent to be mixed and made into coating;
Above-mentioned coating is coated in to Q235 steel surface and forms the self-healing coating with iron rust transformation function.
Embodiment 2
Get mass fraction and be 10% nanometer SiO2Dispersion liquid, mixes with polymine (PEI) solution of 5g/L, and uniform stirring, centrifugation, obtain SiO2/ PEI. Get SiO2/ PEI particle mixes with tannic acid (TA) solution of 1g/L, and uniform stirring, centrifugation, obtain SiO2/ PEI/TA; Repeat above-mentioned steps three times, obtain encapsulating the nano container of converting agent of iron rust tannic acid.
Get mass fraction and be 10% nanometer SiO2Dispersion liquid, mixes with polymine (PEI) solution of 5g/L, and uniform stirring, centrifugation, obtain SiO2/ PEI. Get SiO2/ PEI particle mixes with corrosion inhibiter (INH) solution of 1g/L, and uniform stirring, centrifugation, obtain SiO2/ PEI/INH; Repeat above-mentioned steps three times, obtain encapsulating the nano container of corrosion inhibiter.
Get the nano container 1g of above-mentioned encapsulation converting agent of iron rust, the nano container 1g of encapsulation corrosion inhibiter, epoxy resin 20g, is distributed in epoxy resin; Add again 10g epoxy curing agent to be mixed and made into coating;
Above-mentioned coating is coated in to Q235 steel surface and forms the coatings with iron rust transformation function.
Claims (6)
1. one kind has the coatings of iron rust transformation function; it is characterized in that; converting agent of iron rust can transform loose iron rust before corrosion inhibiter film forming; the corrosion inhibiter that coatings is discharged directly generates fine and close diaphragm at steel surface, thereby greatly strengthens the protection effect of coatings.
2. there is the preparation method of the coatings of iron rust transformation function, it is characterized in that, adopt the nano container of the encapsulation of self-assembly method preparation layer by layer converting agent of iron rust, the nano container of encapsulation converting agent of iron rust and corrosion inhibiter is distributed in epoxy resin, epoxy resin and a certain amount of epoxy curing agent are mixed and made into coating, coating are coated in to steel surface and form the self-healing coating with iron rust transformation function.
3. corrosion inhibiter according to claim 2 adopts the mixture of BTA, oxine and poly-aspartate.
4. the mass ratio of the nano container of the nano container of encapsulation converting agent of iron rust according to claim 2 and encapsulation corrosion inhibiter is 1:1.
5. encapsulating according to claim 2 the nano container of corrosion inhibiter and the mass ratio of epoxy resin is 1:10-20.
6. the mass ratio of epoxy curing agent according to claim 2 and epoxy resin is 1:2.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610154870.3A CN105585939B (en) | 2016-03-18 | 2016-03-18 | A kind of coatings with rust transformation and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610154870.3A CN105585939B (en) | 2016-03-18 | 2016-03-18 | A kind of coatings with rust transformation and preparation method thereof |
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| CN105585939A true CN105585939A (en) | 2016-05-18 |
| CN105585939B CN105585939B (en) | 2018-05-22 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107446464A (en) * | 2017-07-20 | 2017-12-08 | 中国科学院过程工程研究所 | Polymeric coating material and preparation method with Corrosion monitoring and self-repair function |
| WO2020034141A1 (en) * | 2018-08-16 | 2020-02-20 | 中国科学院宁波材料技术与工程研究所 | Graphene nano-container-based coating material and self-repairing coating layer, preparation method therefor, and application thereof |
| CN110835488A (en) * | 2018-08-16 | 2020-02-25 | 中国科学院宁波材料技术与工程研究所 | Coating based on graphene nano container, self-repairing coating and preparation method and application thereof |
| CN113773709A (en) * | 2021-09-03 | 2021-12-10 | 北京科技大学 | Self-warning and self-repairing dual-functional coating based on natural polyphenol filler and preparation |
| CN114507468A (en) * | 2020-11-16 | 2022-05-17 | 天津大学 | Magnesium alloy surface photo-thermal self-repairing coating and preparation method thereof |
| CN117777820A (en) * | 2024-02-28 | 2024-03-29 | 太原理工大学 | Reversible self-early warning and self-repairing coating and preparation method thereof |
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2016
- 2016-03-18 CN CN201610154870.3A patent/CN105585939B/en not_active Expired - Fee Related
Patent Citations (3)
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Non-Patent Citations (1)
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107446464A (en) * | 2017-07-20 | 2017-12-08 | 中国科学院过程工程研究所 | Polymeric coating material and preparation method with Corrosion monitoring and self-repair function |
| CN107446464B (en) * | 2017-07-20 | 2019-07-19 | 中国科学院过程工程研究所 | Polymeric coating material and preparation method with Corrosion monitoring and self-repair function |
| WO2020034141A1 (en) * | 2018-08-16 | 2020-02-20 | 中国科学院宁波材料技术与工程研究所 | Graphene nano-container-based coating material and self-repairing coating layer, preparation method therefor, and application thereof |
| CN110835488A (en) * | 2018-08-16 | 2020-02-25 | 中国科学院宁波材料技术与工程研究所 | Coating based on graphene nano container, self-repairing coating and preparation method and application thereof |
| CN110835488B (en) * | 2018-08-16 | 2021-11-16 | 中国科学院宁波材料技术与工程研究所 | Coating based on graphene nano container, self-repairing coating and preparation method and application thereof |
| CN114507468A (en) * | 2020-11-16 | 2022-05-17 | 天津大学 | Magnesium alloy surface photo-thermal self-repairing coating and preparation method thereof |
| CN114507468B (en) * | 2020-11-16 | 2022-12-13 | 天津大学 | Magnesium alloy surface photo-thermal self-repairing coating and preparation method thereof |
| CN113773709A (en) * | 2021-09-03 | 2021-12-10 | 北京科技大学 | Self-warning and self-repairing dual-functional coating based on natural polyphenol filler and preparation |
| CN117777820A (en) * | 2024-02-28 | 2024-03-29 | 太原理工大学 | Reversible self-early warning and self-repairing coating and preparation method thereof |
| CN117777820B (en) * | 2024-02-28 | 2024-05-31 | 太原理工大学 | Reversible self-early warning and self-repairing coating and preparation method thereof |
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Granted publication date: 20180522 Termination date: 20190318 |