CN112126263A - Preparation method of self-repairing long-acting anti-corrosion material and self-repairing long-acting anti-corrosion film layer on surface of substrate - Google Patents
Preparation method of self-repairing long-acting anti-corrosion material and self-repairing long-acting anti-corrosion film layer on surface of substrate Download PDFInfo
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- 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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- 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
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- 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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- 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
- C09D191/00—Coating compositions based on oils, fats or waxes; Coating compositions based on derivatives thereof
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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
- C09D191/00—Coating compositions based on oils, fats or waxes; Coating compositions based on derivatives thereof
- C09D191/06—Waxes
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- 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
- C09D201/00—Coating compositions based on unspecified macromolecular compounds
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- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- 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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- 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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- 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
- C08K3/38—Boron-containing compounds
- C08K2003/382—Boron-containing compounds and nitrogen
- C08K2003/385—Binary compounds of nitrogen with boron
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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- 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
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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
Abstract
The invention discloses a preparation method of a self-repairing long-acting anticorrosive material. The method disperses the solid-phase two-dimensional sheet material into the liquid-phase material to obtain the mixed material containing the solid phase and the liquid phase, the mixed material has certain fluidity, and has self-repairing capability after being damaged by external influence, and the mixed material has good stability and long-acting corrosion protection performance. The film layer formed on the surface of the substrate by using the mixed material has self-repairing capability and long-acting corrosion protection performance.
Description
Technical Field
The invention relates to the field of self-repairing coatings, in particular to a preparation method of a self-repairing long-acting anticorrosive material and a self-repairing long-acting anticorrosive film layer on the surface of a substrate.
Background
The traditional methods for protecting active metals mainly comprise chemical modification, organic coatings, organic/polymer film coating and the like, but most of the methods easily generate various damages under the external action, so that the original protective performance of the active metals is lost in the service process, and the self-repairing coating technology is developed.
With the ultra-fast development of modern science and technology, especially the development of intelligent material technology, higher requirements are put forward on the preparation of coating materials, and the development of intelligent self-repairing materials becomes a necessary trend. The current intelligent self-repairing material technology mainly focuses on an intrinsic self-repairing material repaired through the chemical reaction of the material after the material is damaged; and the stimulation response type self-repairing material is repaired by external heating, irradiation, soaking and force action.
Disclosure of Invention
Aiming at the technical current situation, the invention provides a preparation method of a self-repairing long-acting anti-corrosion material, and the material prepared by the method can be actively and quickly repaired and restored without responding to external stimulation after being mechanically damaged, and has long-acting anti-corrosion performance.
The technical scheme of the invention is as follows: a preparation method of a self-repairing long-acting anti-corrosion material is characterized by comprising the following steps: and dispersing the solid-phase two-dimensional sheet material into the liquid-phase material to obtain a mixed material containing the solid-phase material and the liquid-phase material, wherein the mixed material has certain fluidity.
The liquid phase material is not limited, and comprises one or a mixture of several of oil, grease, ionic liquid and the like. Wherein, the oil includes but is not limited to one or more of silicone oil, vegetable oil, mineral oil and the like; the grease includes but is not limited to one or more of resin, grease, silane and the like.
The two-dimensional sheet material and the liquid phase material are mixed and do not react, and the two-dimensional sheet material comprises but is not limited to alkenes and derivatives thereof, transition metal carbon compounds and derivatives thereof, transition metal nitrides and derivatives thereof, transition metal disulfides and derivatives thereof, boron nitride and derivatives thereof, glass flakes, mica sheets and organic two-dimensional materials.
The two-dimensional sheet material is not limited in size, and is preferably micron-sized and nanometer-sized.
Preferably, the mixed material is composed of a solid-phase material and a liquid-phase material.
The method for dispersing the solid-phase two-dimensional lamellar material into the liquid-phase material is not limited, and can be one or more of stirring, ultrasonic oscillation, shaking, rotation and the like.
The solid-phase two-dimensional sheet material is dispersed into the liquid-phase material, the two-dimensional sheet material forms a dispersed structure with a labyrinth network, a layer-by-layer arrangement structure, an interpenetration structure, a stacking structure and the like in the liquid-phase material, the viscosity of the liquid-phase material is improved, meanwhile, the mixed material containing the solid-phase material and the liquid-phase material still has certain fluidity, various dispersed structures formed by the two-dimensional sheet material can block and shield the diffusion and permeation processes of corrosive media in a film layer, and the corrosion path is prolonged, so that the stability and the corrosion protection performance of the mixed material are improved; the liquid phase still has certain fluidity, so that after the mixed material is damaged by external influence, the fluidity of the liquid phase can provide good self-repairing capability for the mixed material, and the damage comprises but is not limited to scratches, abrasion and the like.
Therefore, the mixed material prepared by the preparation method of the invention has autonomous and ultrafast repair capability without external stimulation (such as heating, irradiation, electricity, magnetism, water, external force and PH) after being damaged by external influence, thereby fundamentally solving the problem that the current self-repairing material needs external stimulation responsiveness; in addition, the mixed material also has high corrosion protection performance and excellent corrosion protection capability in corrosive media such as saline, hydrochloric acid, sodium hydroxide, neutral salt spray and the like.
In addition, the liquid phase material and the two-dimensional sheet material used in the invention have wide sources, and the preparation method is simple and feasible, so that the film layer with excellent self-repairing performance and corrosion protection performance can be obtained through common materials without complex pretreatment process, and a new thought is provided for the preparation of the self-repairing anticorrosive material.
When the mixed material prepared by the preparation method is used for forming a film layer on the surface of a substrate, the film layer has autonomous and ultrafast repair capability without external stimulation (such as heating, irradiation, electricity, magnetism, water, external force and PH) after being damaged by external influence, and simultaneously has good corrosion protection performance and good corrosion protection capability in corrosive media such as saline water, hydrochloric acid, sodium hydroxide, neutral salt spray and the like. The method for forming the film layer on the surface of the substrate by the mixed material is not limited, and comprises one or more of coating, tape casting, printing, spraying, spin coating and the like.
Drawings
FIG. 1 is a scanning electron microscope image of a two-dimensional sheet material selected for use in example 1.
FIG. 2 is a transmission electron microscope photograph of the two-dimensional lamellar material dispersed in ionic liquid in example 1.
Fig. 3 is a picture of a process of repairing scratches of the film layer manufactured in example 1.
FIG. 4 is a comparison of the morphology of the film prepared in example 1 before soaking in 1mol/L saline and after soaking for 240 hours.
FIG. 5 is a comparison of the morphology of the film layer prepared in example 1 before and after soaking in 1mol/L hydrochloric acid for 240 hours.
FIG. 6 is a comparison of the morphology of the film prepared in example 1 before soaking in 1mol/L NaOH and after soaking for 240 hours.
FIG. 7 is a comparison of the profile of the film prepared in example 1 before etching in neutral salt spray for 240 hours.
Detailed Description
The present invention will be described in further detail with reference to the following examples and drawings, which are intended to facilitate the understanding of the present invention and are not intended to limit the present invention in any way.
Example 1:
a scanning electron micrograph of the two-dimensional micro/nano-scale solid lamellar hexagonal boron nitride is shown in figure 1, and the hexagonal boron nitride is in micro/nano-scale lamellar distribution.
Dispersing the two-dimensional micro/nano-scale solid lamellar hexagonal boron nitride into ionic liquid, stirring for 30min at 25 ℃, then ultrasonically dispersing for 60min at 65 ℃, vacuumizing in the ultrasonic process to remove air on the interface of the hexagonal boron nitride and the ionic liquid to obtain a mixed material, wherein solid-phase particles in the mixed material are uniformly dispersed in a liquid phase and do not agglomerate. The transmission electron micrograph of the mixed material is shown in fig. 2, which illustrates that the solid phase sheet material forms a laminated structure in a liquid phase after simple dispersion.
And coating the mixed material on a metal substrate to form a film layer. Then, as shown in fig. 3 (a), the film layer is scratched even if the scratch width reaches the millimeter level (1.25 mm); after 5 seconds, the scratch is gradually healed as shown in (b) of fig. 3; after 20s, the scratch is substantially repaired as shown in (c) of fig. 3.
The prepared membrane layer is soaked in 1mol/L saline water for 240 hours, and the topography of the membrane layer before and after soaking is shown in figure 4.
The prepared film layer is soaked in 1mol/L hydrochloric acid for 240 hours, and the topography of the film layer before and after soaking is shown in figure 5.
The prepared film layer is soaked in 1mol/L sodium hydroxide for 240 hours, and the topography of the film layer before and after soaking is shown in figure 6.
The prepared film layer is placed in neutral salt spray for corrosion for 240 hours, and the topography of the film layer before and after corrosion is shown in figure 7.
Wherein the bright spots in the left images of fig. 4, 5, 6 and 7 are formed by the reflection of light when the surface concave-convex structure of the film layer is taken; while the absence of bright spots in the right image is due to the sample being photographed in an etching solution at this time.
As can be seen from the morphology photographs before and after the immersion corrosion and the salt spray corrosion in fig. 4, 5, 6, and 7, the metal substrate is corroded in different degrees, and the region covered by the film layer is not corroded significantly, which indicates that the film layer prepared in the embodiment has not only a self-repairing capability but also an excellent long-term corrosion protection capability.
Example 2:
dispersing two-dimensional nano solid lamellar graphene oxide into liquid phase material lubricating oil, stirring for 60min at 15 ℃, then ultrasonically shaking for 45min at 70 ℃, vacuumizing in the ultrasonic process to remove air on the interface of graphene oxide and lubricating oil, and obtaining a mixed material, wherein the solid phase lamellar material in the mixed material is uniformly dispersed in the liquid phase and does not agglomerate. After the mixed material is dispersed, the solid phase sheet material forms a layer-by-layer arrangement structure in a liquid phase.
And coating the mixed material on a metal substrate to form a film layer. Then, even if the scratch width reaches millimeter level, the scratch can be basically repaired after about 15s, which shows that the film has the rapid self-repairing capability.
Similar to example 1, the film prepared above was soaked in 1mol/L saline water for 240 hours, soaked in 1mol/L hydrochloric acid for 240 hours, soaked in 1mol/L sodium hydroxide for 240 hours, and subjected to neutral salt spray corrosion for 240 hours, and it was found that no significant corrosion occurred in the area covered by the film before and after the soaking corrosion and the salt spray corrosion, indicating that the film had long-lasting corrosion protection capability.
Example 3:
two-dimensional micron-sized solid lamellar materials (glass flakes) are selected and dispersed in liquid phase material silane, the liquid phase material silane is vibrated for 60min at the temperature of 30 ℃, then the liquid phase material silane is ultrasonically dispersed for 75min at the temperature of 55 ℃, air on the interface of the glass flakes and the silane is removed by vacuumizing in the ultrasonic process, and a mixed material is obtained, wherein the solid phase lamellar materials in the mixed material are uniformly dispersed in the liquid phase and do not agglomerate. The transmission electron microscope photo of the mixed material shows that the dispersed solid phase particles form an interpenetration structure in the liquid phase.
And coating the mixed material on a metal substrate to form a film layer. Then, the film layer is scratched, even if the scratch width reaches a millimeter level, the scratch can be basically repaired after about 18 seconds, and the film layer has the rapid self-repairing capability.
Similar to example 1, the film prepared above was soaked in 1mol/L saline water for 240 hours, soaked in 1mol/L hydrochloric acid for 240 hours, soaked in 1mol/L sodium hydroxide for 240 hours, and subjected to neutral salt spray corrosion for 240 hours, and it was found that no significant corrosion occurred in the area covered by the film before and after the soaking corrosion and the salt spray corrosion, indicating that the film had long-lasting corrosion protection capability.
Example 4:
the preparation method comprises the steps of selecting a two-dimensional micron-sized solid lamellar material (mica), dispersing the two-dimensional micron-sized solid lamellar material into liquid-phase material vegetable oil, oscillating for 55min at 15 ℃, then ultrasonically dispersing for 35min at 70 ℃, vacuumizing in the ultrasonic process to remove air on an interface between the mica and silane, and obtaining a mixed material, wherein the solid lamellar material in the mixed material is uniformly dispersed in a liquid phase and does not agglomerate. The transmission electron microscope photograph of the mixed material shows that the dispersed solid phase particles form a stacked labyrinth structure in the liquid phase.
And coating the mixed material on a metal substrate to form a film layer. Then, the film layer is scratched, even if the scratch width reaches a millimeter level, the scratch can be basically repaired after about 16 seconds, and the film layer has the rapid self-repairing capability.
The embodiments described above are intended to illustrate the technical solutions of the present invention in detail, and it should be understood that the above-mentioned embodiments are only specific embodiments of the present invention, and are not intended to limit the present invention, and any modification, supplement or similar substitution made within the scope of the principles of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The preparation method of the self-repairing long-acting anti-corrosion material is characterized by comprising the following steps: and dispersing the solid-phase two-dimensional sheet material into the liquid-phase material to obtain a mixed material containing the solid phase and the liquid phase, wherein the mixed material has certain fluidity.
2. The method for preparing the self-repairing long-acting anti-corrosion material as claimed in claim 1, which is characterized in that: the liquid phase material comprises one or a mixture of more of oil, grease and ionic liquid;
preferably, the oil comprises one or more of silicone oil, vegetable oil and mineral oil;
preferably, the grease includes resin, grease, silane, epoxy resin.
3. The method for preparing the self-repairing long-acting anti-corrosion material as claimed in claim 1, which is characterized in that: the two-dimensional sheet material comprises one or a mixture of more of alkenes and derivatives thereof, transition metal carbon compounds and derivatives thereof, transition metal nitrides and derivatives thereof, transition metal disulfides and derivatives thereof, boron nitride and derivatives thereof, glass flakes, mica sheets and organic two-dimensional materials.
4. The method for preparing the self-repairing long-acting anti-corrosion material as claimed in claim 1, which is characterized in that: the size of the two-dimensional sheet material is micron-scale or nanometer-scale.
5. The method for preparing the self-repairing long-acting anti-corrosion material as claimed in claim 1, which is characterized in that: the solid-phase two-dimensional sheet material is dispersed into the liquid-phase material to form a dispersion structure of a labyrinth network, a layer-by-layer arrangement structure, an interpenetration structure and a stacking structure;
preferably, the method for dispersing the solid-phase two-dimensional lamellar material into the liquid-phase material is one or more of stirring, ultrasonic oscillation, shaking and rotation.
6. The method for preparing the self-repairing long-acting anti-corrosion material as claimed in claim 1, which is characterized in that: the mixed material can be actively repaired and restored without external stimulus response after being damaged by the outside.
7. The method for preparing the self-repairing long-acting anti-corrosion material as claimed in claim 1, which is characterized in that: the mixed material has long-acting corrosion protection performance.
8. The method for preparing the self-repairing long-acting anti-corrosion material as claimed in claim 7, which is characterized in that: the mixed material has long-acting corrosion protection performance in saline water, hydrochloric acid, sodium hydroxide and neutral salt spray.
9. A self-repairing long-acting anti-corrosion film layer on the surface of a substrate is characterized in that: a mixed material prepared by the method of any one of claims 1 to 8 is used for forming a film layer on the surface of a substrate.
10. A self-repairing long-acting anti-corrosion film layer on the surface of a substrate is characterized in that: the method for forming the film layer on the surface of the substrate by the mixed material comprises one or more of coating, tape casting, spin coating and spraying.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113004776A (en) * | 2021-02-03 | 2021-06-22 | 中山大学 | Water-based self-repairing coating and application thereof |
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| CN113004776A (en) * | 2021-02-03 | 2021-06-22 | 中山大学 | Water-based self-repairing coating and application thereof |
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Application publication date: 20201225 |