CN110142190A - Selfreparing composite coating and its application and anticorrosion material and preparation method thereof - Google Patents
Selfreparing composite coating and its application and anticorrosion material and preparation method thereof Download PDFInfo
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- CN110142190A CN110142190A CN201910472888.1A CN201910472888A CN110142190A CN 110142190 A CN110142190 A CN 110142190A CN 201910472888 A CN201910472888 A CN 201910472888A CN 110142190 A CN110142190 A CN 110142190A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/52—Two layers
- B05D7/54—No clear coat specified
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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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Abstract
The present invention provides a kind of selfreparing composite coating and its application and anticorrosion material and preparation method thereof.The selfreparing composite coating includes: the hydrophobic layer and hydrophilic layer being in contact, wherein the hydrophobic layer includes lyophobic dust；The hydrophilic layer includes reconditioning layer, and the reconditioning layer includes hydroaropic substance A, and the hydroaropic substance A includes at least one of dynamic covalent bond.Compared with prior art the invention has the benefit that selfreparing composite coating of the invention can be applied in anticorrosion field, will not make Liquid Penetrant and can active reparation making and using the defects of process, to effectively play etch-proof effect.Further, the selfreparing composite coating in anticorrosion material of the invention, liquid will not enter in composite coating the etched the matrix with substrate contact, and can active reparation making and using the defects of process and there is excellent biocompatibility.
Description
Technical field
The present invention relates to the technical fields of chemical material and application, more particularly to a kind of selfreparing composite coating and its answer
With with anticorrosion material and preparation method thereof.
Background technique
Many materials (such as metal, plastics etc.) in daily life corrosion easily occurs under the action of external environment and to state
The people carry out massive losses in economy-zone.For the anticorrosion research of metal, using chemical conversion layer, differential arc oxidation, anodic oxidation, plating
Organic and inorganic or polymeric coating layer is coated on metal surface etc. various technologies, so metal is isolated with corrosive medium from
And reach etch-proof purpose.
Although the above method plays protective action to metal to a certain extent, there are still very in actual use
More problems prevents it from stopping corrosive liquid completely if coating is commonly present inevitable pore defect during the preparation process
Invasion, and then the position of Liquid Penetrant occur spot corrosion cause stress to concentrate, be broken in point corrosion pit position, so that metal
Service life cut down significantly.Make up its pore defect conventional method be by repeatedly coating, however it is this simple " plug-hole "
It is tactful and non-perfect, repeatedly coating be easy to cause overweight coating, adhesion strength be deteriorated and from metal surface peel off, cause exposed section
Corrosion aggravation.
In recent years, scientist has found that determining for liquid may be implemented in the asymmetric wetability of Janus film or asymmetric micro-structure
To infiltration, and then achieve the purpose that draining or water suction.That is hydrophobic layer is upper, and when hydrophilic layer is under, drop spreads are in Janus film
Surface is impermeable, thus the characteristics of its liquid will not be permeated applied to the anticorrosion of material in terms of there is certain prospect.But
It is, although the introducing of Janus theory can significantly delay substrate to contact with the direct of corrosive medium, this passive protection
Method cannot incude the variation of external environment in time, if may meet in use without timely and effectively reparation
Breakage and cracking, these defects the adhesive force of coating can then significantly reduced, and then make corrosion aggravate, reduce the use of material
Service life.
In the prior art, the film forming matter of itself can be relied on using self-repair material or respond the chemistry of external environment
Key realizes that actively repairing defect caused by corrosion reaches etch-proof purpose with this, still, the remediation efficiency of self-repair material
It is limited, and influence the long-lasting protection performance of coating entirety.
Citation [1] provides the preparation method that iron film is covered in a kind of anticorrosion.This method passes through ascorbic acid and inositol
Corrosion inhibiter is made in six phosphatase reactions, has the characteristics that using ascorbic acid less toxic or nontoxic, cheap, and oxygen atom is again in molecule
With stronger electron donation, firm absorption protective film can be formed in metal surface, can be stabilized under alkaline condition,
When being contacted with each other after in conjunction with phytic acid using phosphoric acid ester molecule and material surface, the hydrophobic chain in molecule is adsorbed on material
Surface, form continuous adsorption layer, hydrophilic group towards air because in its molecule contain-OH, can be formed with hydrone
Hydrogen bond, the water layer being adsorbed will form conductive film, enhance the electric conductivity of material surface, to reduce the electrostatic of material surface
Lotus gathers, and extends the permeation pathway that oxygen molecule reaches matrix surface, has excellent barrier properties, improves anticorrosion
Performance.But preparation method is complicated, although having certain Corrosion Protection, it still has pore defect, cannot
Stop the invasion of corrosive liquid completely.
Citation [2] provides one kind can be automatically repaired erosion shield and preparation method thereof in acidic environment.This can
Be automatically repaired erosion shield, include following part: load corrosion inhibiter the responsibility mesoporous silica 0.5-5 parts by weight of acid and
Resin cured matter 95-99.5 parts by weight.But this can be automatically repaired erosion shield and just can be achieved to repair automatically in acidic environment
It is multiple, corresponding acid cannot be provided in other environment, the corrosion inhibiter of load cannot discharge rapidly out, can not form protection
Film cannot inhibit to corrode.
From this, how to construct the protection system for being really suitable for material, become a kind of technical problem urgently to be resolved.
Citation [1]: CN108997604A
Citation [2]: CN109504242A
Summary of the invention
Problems to be solved by the invention
For the technical problems in the prior art, present invention firstly provides a kind of selfreparing composite coatings in anti-corrosion
Application in erosion.
Further, the anticorrosion the present invention also provides a kind of selfreparing composite coating and comprising the selfreparing composite coating
Material, which will not make Liquid Penetrant and can actively repair damage location, to effectively play anticorrosion
Effect.
Further, the present invention also provides a kind of preparation methods of anticorrosion material.
The solution to the problem
The present invention provides a kind of application of selfreparing composite coating in anticorrosion, wherein the selfreparing composite coating
It include: the hydrophobic layer and hydrophilic layer being in contact, wherein
The hydrophobic layer includes lyophobic dust；
The hydrophilic layer includes reconditioning layer, and the reconditioning layer includes hydroaropic substance A, the hydroaropic substance A packet
At least one of covalent bond containing dynamic.
Application of the selfreparing composite coating according to the present invention in anticorrosion, wherein the hydrophilic layer also include with
The transition zone that the reconditioning layer is in contact；Wherein
The transition zone is present between the reconditioning layer and the hydrophobic layer or the transition zone be present in it is described
The side opposite with the hydrophobic layer of reconditioning layer；
The transition zone includes hydroaropic substance.
Application of the selfreparing composite coating according to the present invention in anticorrosion, wherein the hydrophobic layer is doped with inhibition
Agent, it is preferable that the corrosion inhibiter includes the combination of one or more of Paeonol, honey, orange peel and leaf of bamboo.
Application of the selfreparing composite coating according to the present invention in anticorrosion, wherein the selfreparing composite coating
Surface has irregular structure, it is preferable that the irregular structure includes in sunk structure, bulge-structure and reticular structure
It is at least one.
Application of the selfreparing composite coating according to the present invention in anticorrosion, wherein the dynamic covalent bond includes acyl
At least one of amine key, cystine linkage, imine linkage and acylhydrazone key.
The present invention also provides a kind of selfreparing composite coatings, wherein the selfreparing composite coating is in claim 1-5
Described in any item selfreparing composite coatings.
The present invention also provides a kind of anticorrosion materials, wherein the anticorrosion material includes matrix and is formed in the base
The selfreparing composite coating in body surface face；The selfreparing composite coating is selfreparing composite coating as claimed in claim 6.
Anticorrosion material according to the present invention, wherein the selfreparing composite coating is formed in the surface of described matrix, institute
It states hydrophobic layer to be in contact with the surface of described matrix, the hydrophilic layer is set to one opposite with described matrix of the hydrophobic layer
Side；Or
The hydrophilic layer is in contact with the surface of described matrix, and the hydrophobic layer is being set to the hydrophilic layer with the base
The opposite side of body.
Anticorrosion material according to the present invention, wherein described matrix is surface treated matrix；Preferably, matrix passes through
After surface treatment, the surface of matrix has reticular structure.
The present invention also provides a kind of preparation methods of anticorrosion material according to the present invention comprising:
Hydroaropic substance A is taken to prepare reconditioning layer material；
Lyophobic dust is taken to prepare hydrophobic material；
The reconditioning layer material and the hydrophobic material is set to be alternatively formed hydrophilic layer and hydrophobic layer on the surface of matrix,
The hydrophilic layer includes reconditioning layer.
The preparation method of anticorrosion material according to the present invention, wherein the preparation method further includes taking hydroaropic substance
Prepare buffer layer material；
Transition zone is formed between the reconditioning layer and the hydrophobic layer using the buffer layer material；Or utilize institute
It states buffer layer material and forms transition zone in the side opposite with the hydrophobic layer of the reconditioning layer.
Preparation method according to the present invention, wherein the preparation method further includes being surface-treated to described matrix；It is excellent
Selection of land is modified processing using surface of the modifying agent to described matrix；The modifying agent includes acid solution；
It is highly preferred that the modifying agent also includes alcohols and/or inorganic salts.
The effect of invention
Compared with prior art the invention has the benefit that selfreparing composite coating of the invention can be applied in anti-corrosion
Erosion field, will not make Liquid Penetrant and can active reparation making and using the defects of process, to effectively play
Etch-proof effect.
Further, the selfreparing composite coating in anticorrosion material of the invention, liquid will not enter in composite coating
The etched the matrix with substrate contact, and can active reparation making and using the defects of process and having excellent
Biocompatibility.
Further, the preparation method of anticorrosion material of the invention, used raw material are easy to get, safety with higher
Property, molding is easier to, and process time is shorter, and production efficiency is higher, is more suitble to the production of industrial-scale.
Detailed description of the invention
Fig. 1 is the three-dimensional structure diagram of the anticorrosion material of an embodiment of the present invention；
Fig. 2 is the three-dimensional structure diagram of the anticorrosion material of an embodiment of the present invention；
Fig. 3 is the Electronic Speculum of the magnesium ingot of the embodiment of the present invention 2 and the anticorrosion material VIII (Mg-P@PCL-PGD) of embodiment 3
Figure；
Fig. 4 is the big logotype of contact angle of the different materials of the embodiment of the present invention 1；
Fig. 5 is the big logotype of contact angle of the embodiment of the present invention 2 and the different materials in embodiment 3；
Fig. 6 is the anticorrosion material VIII (Mg-P@PCL-PGD) of magnesium ingot and embodiment 3 of the invention in the selfreparing of 0h
Situation schematic diagram；
Fig. 7 is the anticorrosion material VIII (Mg-P@PCL-PGD) of magnesium ingot and embodiment 3 of the invention in the selfreparing of 72h
Situation schematic diagram；
Fig. 8 is anticorrosion material VIII (Mg-P@PCL-PGD) reviewing one's lessons by oneself in 216h of magnesium ingot and embodiment 3 of the invention
Multiple situation schematic diagram；
Fig. 9 be magnesium ingot and embodiment 3 of the invention anticorrosion material VIII (Mg-P@PCL-PGD) 372h it is rotten from
Repair situation schematic diagram；
Figure 10 is anticorrosion material VIII (Mg-P@PCL-PGD) reviewing one's lessons by oneself in 468h of magnesium ingot and embodiment 3 of the invention
Multiple situation schematic diagram；
Figure 11 is that the change in impedance value in different time of the embodiment of the present invention 2 and the different materials in embodiment 3 becomes
Gesture figure.
Description of symbols
1: matrix；2: hydrophobic layer；3: hydrophilic layer；4: selfreparing composite coating；
31: reconditioning layer；32: transition zone.
Specific embodiment
It will be detailed below various exemplary embodiments, feature and aspect of the invention.Dedicated word " example herein
Property " mean " being used as example, embodiment or illustrative ".Here as any embodiment illustrated by " exemplary " should not necessarily be construed as
Preferred or advantageous over other embodiments.
In addition, in order to better illustrate the present invention, numerous details is given in specific embodiment below.
It will be appreciated by those skilled in the art that without certain details, the present invention equally be can be implemented.In other example,
Method well known to those skilled in the art, means, equipment and step are not described in detail, in order to highlight master of the invention
Purport.
Such as without Special Statement, unit used in the present invention is SI units, and the number occurred in the present invention
Value, numberical range should all be interpreted as containing the inevitable Systematic Errors of institute in industrial production.
Such as without Special Statement, the present invention can be mistake if any " substantially " that uses, similar word, the meaning such as " basic "
Difference is no more than 5%.
First embodiment
First embodiment of the invention provides a kind of selfreparing composite coating 4 and the selfreparing composite coating 4 exists
Application in anticorrosion.As shown in Figure 1, the selfreparing composite coating 4 of the invention includes: the hydrophobic layer 2 being in contact and parent
Water layer 3, wherein
The hydrophobic layer 2 includes lyophobic dust；
The hydrophilic layer 3 includes reconditioning layer 31, includes hydroaropic substance A, the hydrophily in the reconditioning layer 31
Combination comprising one or more of dynamic covalent bond in substance A.
In a kind of specific embodiment, as shown in Fig. 2, the hydrophilic layer 3 also includes and the reconditioning layer 31
The transition zone 32 being in contact, wherein the transition zone 32 is present between the reconditioning layer 31 and the hydrophobic layer 2, Huo Zhesuo
State the side opposite with the hydrophobic layer 2 that transition zone 32 is present in the reconditioning layer 31；The transition zone 32 includes hydrophilic
Property substance.
In the present invention, the selfreparing composite coating 4 is formed in the surface of matrix 1, the hydrophobic layer 2 and described matrix
1 surface is in contact, and the hydrophilic layer 3 is set to the side opposite with described matrix 1 of the hydrophobic layer 2；Or
The hydrophilic layer 3 is in contact with the surface of described matrix 1, the hydrophobic layer 2 be set to the hydrophilic layer 3 with institute
State the opposite side of matrix 1.
Hydrophilic layer 3 and hydrophobic layer 2 of the invention all has good biocompatibility, obtained selfreparing composite coating 4
Also there is excellent biocompatibility, excellent anticorrosion ability can be obtained.
Selfreparing composite coating 4 of the invention prevents liquid under the collective effect of static pressure and capillary force in hydrophobic forces
Body penetrates, and then reaches etch-proof purpose.Selfreparing composite coating 4 of the invention can also actively repair damage location, real
Now to the dual reparation of damage location.Selfreparing composite coating 4 of the invention by water will not permeation coating characteristic with active repair
The advantages of multiple damage location, combines, so as to effectively play corrosion-resisting function.
Selfreparing composite coating 4 of the invention is able to respond ion caused by corrosion and is complexed therewith, is able to respond corruption
Alkaline condition caused by losing realizes selfreparing with this.
<selfreparing composite coating>
Selfreparing composite coating 4 of the invention can be a kind of Janus film with self-repair function.Janus film is general
Refer to the film with dissymmetrical structure or property, the key of difference Janus film and general asymmetric membrane is the property on film two sides
Whether matter " opposes ", such as hydrophilic/hydrophobic or lotus electropositive/bear are electrically, and in simple structure or composition not
Janus film cannot be symmetrically referred to as.Selfreparing composite coating 4 of the invention has two sides of different nature, that is, has Janus knot
Structure and the ability simultaneously with selfreparing, and the function of the two can be played simultaneously.Selfreparing composite coating 4 is in hydrophobic effect
Penetration by liquid can be prevented under the collective effect of power, static pressure and capillary force, and then reaches etch-proof purpose.It is of the invention from
Repairing hydrophilic layer 3 and hydrophobic layer 2 in composite coating 4 can have self-reparing capability to realizing selfreparing, can with it is above-mentioned
Janus structure, which combines, reaches dual erosion-resisting purpose.
In the present invention, selfreparing composite coating 4 can be prepared by two methods: asymmetry preparation and asymmetry
Decoration, wherein asymmetric preparation is that Janus structure is formed during film is formed, and asymmetric decoration is modified by the later period to obtain
Obtain Janus structure.
Asymmetry preparation is to prepare two kinds of dissymmetrical structures respectively, is then bonded together two kinds of dissymmetrical structures, with
Obtain Janus structure.Such as: hydrophobic layer 2 and hydrophilic layer 3 can be prepared by the method for electrostatic spinning, to obtain Janus knot
Structure；Hydrophilic component and hydrophobic components can also be deposited in substrate by way of directly coating and prepare hydrophobic layer 2 and parent
Water layer 3, to obtain Janus structure.
In addition, asymmetric modification can also be by the modified method of single side to obtain Janus structure.Such as: it can pass through
Ultraviolet lighting, the methods of chemical vapor deposition and co-deposition have the selfreparing composite coating 4 of Janus structure to obtain.This hair
It is bright that the hydrophilic layer 3 of selfreparing composite coating 4, the preparation method of hydrophobic layer 2 are not particularly limited, as long as can obtain corresponding
Janus structure with hydrophilic layer 3 and hydrophobic layer 2.
Further, the surface of selfreparing composite coating 4 of the invention and/or inside have multiple pore structures, the hole
The aperture of structure is 0.1-1000nm；In selfreparing composite coating 4 of the invention, hydrophobic layer 2 and hydrophilic layer 3 can be close
It is combined together, to play selfreparing and etch-proof purpose.In the present invention, the surface of the selfreparing composite coating 4
There can also be multiple irregular structures.Irregular structure for example may is that in sunk structure, bulge-structure, reticular structure etc.
At least one.
<hydrophobic layer>
In the present invention, hydrophobic layer 2 contains lyophobic dust, and lyophobic dust can be containing hydrophobic group, and have
There is hydrophobic substance, such as: it can be the chemical substance of the alkyl containing C10~C20, can be containing aryl, ester group, ether
The chemical substance of the alkyl of the groups such as base, amido and amide groups can also be the chemical substance of alkyl containing double bonds；It can also be with
It is the chemical substance etc. containing ester group；Preferably, lyophobic dust may include aliphatic polyester, and such as: polycaprolactone gathers
Second lactone, polylactide and polymeric polyglycolide-polylactide etc..
Preferably, corrosion inhibiter can be adulterated in hydrophobic layer 2 of the invention, to further increase anti-corrosion capability.Specifically
Ground, the corrosion inhibiter adulterated may include inorganic inhibitor and/or organic inhibitor.Inorganic inhibitor mainly include chromate,
Nitrite, silicate, molybdate, tungstates, Quadrafos and zinc salt etc.；Organic inhibitor mainly includes phosphonic acids (salt), phosphine
Some heterocyclic compounds containing oxynitrides such as carboxylic acid, coloured glaze base benzothiazole, benzotriazole and lignosulfonate.In addition, having
Machine corrosion inhibiter can also be polymerization species corrosion inhibiter.Such as: it can be including polyethylene kind, copolymer of phosphono carboxylic acid (POCA)
With the polymer chemistry object of some oligomer such as poly-aspartate.
In the present invention, corrosion inhibiter may include one or more of Paeonol, honey, orange peel and leaf of bamboo
Combination.
In the present invention, hydrophobic layer 2 and the surface of matrix 1 can be made to be in contact, hydrophilic layer 3 be set to hydrophobic layer 2 with
The opposite side of matrix 1；Hydrophilic layer 3 and the surface of matrix 1 can also be made to be in contact, hydrophobic layer 2 is set to hydrophilic layer 3 and base
The opposite side of body 1；It is preferred that hydrophobic layer 2 and the surface of matrix 1 is made to be in contact, hydrophilic layer 3 be set to hydrophobic layer 2 with matrix 1
Opposite side, so as to effectively reach selfreparing and erosion-resisting purpose.
<hydrophilic layer>
Hydrophilic layer 3 of the invention includes reconditioning layer 31.It include hydroaropic substance A in reconditioning layer 31, it is described hydrophilic
Property substance A also includes at least one of dynamic covalent bond on the basis of with hydrophilic radical.The hydroaropic substance
A can be the hydroaropic substance directly containing at least one of dynamic covalent bond, be also possible to when preparing reconditioning layer 31,
The hydroaropic substance containing at least one of dynamic covalent bond is generated, to form reconditioning layer 31.
Preferably, the dynamic covalent bond includes at least one of amido bond, cystine linkage, imine linkage and acylhydrazone key.
For example, it is reacted using carboxylic hydroaropic substance with amino-containing hydroaropic substance and generates amido bond, with
Form reconditioning layer 31.Such as: it can first be soaked in carboxylic hydroaropic substance, then be soaked in amino-containing hydrophily
In substance, to form the reconditioning layer 31 of amide bond；At this point, reconditioning layer can actually be double-layer structure.
Further, as shown in Fig. 2, hydrophilic layer 3 of the invention also includes the transition being in contact with the reconditioning layer
Layer 32, the transition zone 32 is present between the reconditioning layer 31 and the hydrophobic layer 2 or the transition zone 32 is present in
The side opposite with the hydrophobic layer 2 of the reconditioning layer 31, the preferably described transition zone 32 are present in the reconditioning layer 31
Between the hydrophobic layer 2.
It include hydroaropic substance in transition zone 32；Hydroaropic substance can be containing hydrophilic radical and have hydrophily
Substance, such as: can be containing groups such as carboxyl, sulfonic group, sulfate, phosphate, amino, quaternary ammonium group, ether and hydroxyls
Chemical substance；Specifically, in the present invention, hydroaropic substance may include polyacrylic acid, polyurethane, poly-dopamine and poly- second
The combination of one or more of enol etc..
It, can also be doped with suitable corrosion inhibiter in hydrophilic layer of the invention.The corrosion inhibiter is heretofore described delays
Lose agent.In addition, hydroaropic substance A of the invention can be obtained through hydroaropic substance modification.
Second embodiment
Second embodiment of the present invention provides a kind of anticorrosion material.The anticorrosion material includes matrix 1 and shape
At in the selfreparing composite coating 4 on 1 surface of described matrix；The selfreparing composite coating 4 is reviewing one's lessons by oneself in first embodiment
Multiple composite coating 4.
In general, in the present invention, selfreparing composite coating 4 can be formed directly into the surface of matrix 1, to play
The effect of anticorrosion and selfreparing；The present invention previously prepared can also obtain selfreparing composite coating 4, then be positioned in again
The surface of matrix 1, to play the role of etch-proof.
<matrix>
In the present invention, selfreparing composite coating 4 can be formed in the surface of matrix 1, wherein matrix 1 includes metal, pottery
The combination of one or more of porcelain, plastic and glass, wherein metal, which can be in gold, silver, copper, magnesium, iron and aluminium etc., appoints
It anticipates one kind, plastics can be polyethylene and polypropylene etc..
In the present invention, can be by the methods of physically or chemically, being modified to the surface of matrix 1, it for example, can
To be surface-treated using modifying agent to matrix, after being surface-treated, it can make the surface of matrix 1 that there is reticular structure,
So as to preferably be combined as a whole with selfreparing composite coating 4.
The selfreparing composite coating 4 is formed in the surface of described matrix 1, the surface of the hydrophobic layer 2 and described matrix 1
It is in contact, the hydrophilic layer 3 is set to the side opposite with described matrix 1 of the hydrophobic layer 2；Or the hydrophilic layer 3 with
The surface of described matrix 1 is in contact, and the hydrophobic layer 2 is set to the side opposite with described matrix 1 of the hydrophilic layer 3.
Preferably, as shown in Figure 1, in the present invention it is possible to so that hydrophobic layer 2 is in contact with the surface of matrix, hydrophilic layer 3
It is set to the side opposite with described matrix 1 of hydrophobic layer 2, so as to further increase Corrosion Protection.
In addition, the selfreparing composite coating 4 in anticorrosion material of the invention, water will not permeate selfreparing composite coating 4
Characteristic combine with actively repair damage location the advantages of, there is excellent Corrosion Protection and self-healing properties.In addition, should
The biological degradability and adhesiveness of selfreparing composite coating 4 are more excellent, when being implanted into organism, can make cell Proliferation.
Third embodiment
Third embodiment of the present invention provides a kind of preparation method of anticorrosion material, comprising the following steps:
Hydroaropic substance A is taken to prepare reconditioning layer material；
Lyophobic dust is taken to prepare hydrophobic material；
The reconditioning layer material and the hydrophobic material is set to be alternatively formed hydrophilic layer 1 and hydrophobic on the surface of matrix 1
Layer 2, the hydrophilic layer include reconditioning layer 31；
In the present invention, the hydrophobic layer 2 can be made to be in contact with the surface of described matrix 1, the hydrophilic layer 3 is formed in
The side opposite with described matrix 1 of the hydrophobic layer 2；Or the hydrophilic layer 3 is made to be in contact with the surface of described matrix 1,
The hydrophobic layer 2 is formed in the side opposite with described matrix 1 of the hydrophilic layer 3.Preferably, make the hydrophobic layer 2 and institute
The surface for stating matrix 1 is in contact.By the present invention in that hydrophobic material is in contact with matrix 1, it is multiple that selfreparing can be effectively improved
Close the Corrosion Protection of coating 4.
Further, the method also includes:
Hydroaropic substance is taken to prepare buffer layer material；
Transition zone 32 is formed between the reconditioning layer 31 and the hydrophobic layer 2 using the buffer layer material；Or
Transition zone 32 is formed in the side opposite with the hydrophobic layer 2 of the reconditioning layer 31 using the buffer layer material, preferably
Transition zone 32 is formed between the reconditioning layer 31 and hydrophobic layer 2 using the buffer layer material.
In the present invention, the reconditioning layer 31 can be made to be superimposed on opposite with described matrix 1 with the hydrophobic layer 2
On one side, or it is superimposed on the reconditioning layer 31 and transition zone 32 and the one side opposite with described matrix 1 of the hydrophobic layer 2
Surface, form the anticorrosion material.Preferably, in order to make the selfreparing effect of selfreparing composite coating 4 of the invention
It plays, the transition zone 32 is formed between the reconditioning layer 31 and the hydrophobic layer 2.
Specifically, it the described method comprises the following steps:
Hydrophobic material and the surface of matrix 1 is set to be in contact, to form hydrophobic layer 2；
Buffer layer material is taken, the matrix 1 containing hydrophobic layer 2 is placed in the solution of the hydroaropic substance, to be formed
Cross layer 32；
Matrix 1 containing transition zone 32 is placed in described by the solution (that is: reconditioning layer material) for taking the A containing hydroaropic substance
In the solution of hydroaropic substance A, to form reconditioning layer 31.
In general, the solution of the A containing hydroaropic substance can be the aqueous solution of the A containing hydroaropic substance.
Further, it the described method comprises the following steps:
Hydrophobic material and the surface of matrix 1 is set to be in contact, to form hydrophobic layer 2；
Buffer layer material is taken, the matrix 1 containing hydrophobic layer 2 is placed in the solution of the hydroaropic substance, to be formed
Cross layer 32；
The solution of a containing hydroaropic substance and the solution (that is: reconditioning layer material) of a containing hydroaropic substance ' are taken, will be contained
The matrix 1 for crossing layer 32 is placed in the solution of the hydroaropic substance a to be taken out after immersion, is subsequently placed in the molten of a containing hydroaropic substance '
Liquid impregnates, to form reconditioning layer 31；Wherein, hydroaropic substance a and hydroaropic substance a ' react generation include dynamic
The hydroaropic substance A of at least one of covalent bond.
The preparation method of hydrophobic material includes: that lyophobic dust is taken to be dissolved in the first solvent, obtains hydrophobic material.Institute
It states in hydrophobic material, the content of lyophobic dust is 0.1-10wt%.Preferably, inhibition is adulterated in the hydrophobic material
Agent, density of corrosion inhibitor can be 0.001-0.01g/mL.
The preparation method of buffer layer material includes: that hydroaropic substance is taken to be dissolved in the second solvent, obtains buffer layer material,
In, the concentration of hydroaropic substance is 0.1~10mg/mL.In the solution containing hydroaropic substance, pH adjusting agent tune can be used
Its whole pH value is alkalinity, and pH adjusting agent can be NaOH etc..
Reconditioning layer material preparation method may include that the material of the A containing hydroaropic substance is taken to be dissolved in third solvent, obtain
The solution of hydroaropic substance A, wherein the concentration of hydroaropic substance A is 1-10mg/mL.
The preparation method of reconditioning layer material also may include that a containing hydroaropic substance is taken to be dissolved in third solvent, obtain parent
The solution of aqueous substance a, wherein the concentration of hydroaropic substance a is 1-10mg/mL；A' containing hydroaropic substance is taken to be dissolved in third molten
In agent, the solution of hydroaropic substance a ' is obtained, wherein the concentration of hydroaropic substance a ' is 1-10mg/mL.
In the present invention, hydroaropic substance a can be glycol-chitosan and its derivative etc., such as: Propylene Glycol
Chitosan, trimethyl ammonium glycol-chitosan etc.；Hydroaropic substance a ' can be terephthalaldehydic acid-polyethylene glycol and its derivative
Object etc., such as: methoxyl group-terephthalaldehydic acid-polyethylene glycol, terephthalaldehydic acid-polyethylene glycol-terephthalaldehydic acid.
In the present embodiment, the first solvent is the solvent that can dissolve lyophobic dust, such as: methylene chloride, trichlorine
Methane, benzene and tetrahydrofuran etc.；Second solvent is the solvent that can dissolve hydroaropic substance, such as: alcohols or water etc., third is molten
Agent may be alcohols or water etc..
In general, in the present invention, the technique being alternatively formed can be in tiling, coating, immersion, curtain coating and sprinkling
A combination of one or more.
Further, method of the invention further include: the step of matrix 1 is surface-treated；By being carried out to matrix 1
Surface treatment, so as to so that the stronger surface for being attached on matrix 1 of selfreparing composite coating 4.
Preferably, processing is modified using surface of the modifying agent to matrix 1；Modifying agent includes acid solution, it is preferable that
Acid solution includes the combination of one or more of sulfuric acid, hydrochloric acid, nitric acid and phosphoric acid.In the present embodiment, modified
Agent be also possible to include acid solution mixed solution, such as: alcohols (such as: in ethyl alcohol, propyl alcohol, butanol or glycerine etc.
At least one) or inorganic salts etc..
In general, in order not to introduce other impurity, used inorganic salts can be selected consistent with anticorrosion material
Inorganic salts, such as: using Mg metal that can select Mg (NO as matrix 1, and when being modified using nitric acid3)2Make
For inorganic salts ingredients.
Embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.It is not specified in embodiment specific
Condition person carries out according to conventional conditions or manufacturer's recommended conditions.Reagents or instruments used without specified manufacturer is
It can be with conventional products that are commercially available.
Embodiment 1
In the present embodiment, using following copper mesh as substrate.
(1) copper mesh is cut to a length of 3cm, width is the sample of 3cm, obtains matrix Cu, is denoted as Cu；
(2) dichloromethane solution (the corrosion inhibiter Paeonol of doping 0.001g/ml) of the polycaprolactone of 2.5wt% is prepared,
Obtain hydrophobic material.
(3) ethanol solution for preparing the poly-dopamine of 2mg/ml, with sodium hydroxide tune pH to 10.
(4) glycol-chitosan powder is taken, the glycol-chitosan aqueous solution of 4mg/ml is configured to.
(5) terephthalaldehydic acid-polyethylene glycol powder is taken, terephthalaldehydic acid-polyethylene glycol of 4mg/ml is configured to
Aqueous solution.
(6) matrix Cu is soaked in 45s in hydrophobic material, and dry, forms hydrophobic layer；It obtains being provided only with hydrophobic layer
Anticorrosion material I, be denoted as Cu-P@PCL.
(7) matrix Cu is soaked in 12h in the ethanol solution of poly-dopamine, and dry, forms transition zone；It is soaked in second again
15min in the aqueous solution of glycol chitosan, and it is dry, it is then soaked in terephthalaldehydic acid-polyethylene glycol aqueous solution
15min, and it is dry, form reconditioning layer；The anticorrosion material II for being provided only with hydrophilic layer is obtained, Cu-PGD is denoted as.
(8) hydrophobic layer of the above-mentioned anticorrosion material (Cu-P@PCL) for being provided only with hydrophobic layer is bonded in and is provided only with parent
The top of the hydrophilic layer of the anticorrosion material (Cu-PGD) of water layer, obtains anticorrosion material III of the invention, is denoted as Cu-PGD-
P@PCL。
(9) hydrophilic layer of the above-mentioned anticorrosion material (Cu-PGD) for being provided only with hydrophilic layer is bonded in be provided only with it is hydrophobic
The top of the hydrophobic layer of the anticorrosion material (Cu-P@PCL) of layer, obtains anticorrosion material IV of the invention, is denoted as Cu-P@PCL-
PGD。
Embodiment 2
(1) high purity magnesium is cut into having a size of 10mm × 10mm × 2mm sheet substrate, then successively using granularity is 80/
240/1000/3000/5000 sand paper polishing high purity magnesium, the sample with ethanol polished and deionized water cleaning, are denoted as Mg.Electricity
Scarnning mirror picture is shown in the left side Fig. 3.
(2) aqueous solution of modifying agent is prepared, wherein in the aqueous solution of modifying agent, HNO3Concentration be 22g/L, Mg (NO3)2
Concentration be 150g/L, the concentration of ethyl alcohol is 300g/L.Mg is immersed in 60s in modifier solution, later distills sample
Water cleaning, is finally dried at room temperature for, obtains modified matrix Mg, be denoted as Mg-H；
(3) ethanol solution for preparing the poly-dopamine of 2mg/mL, with sodium hydroxide tune pH to 10.
(4) glycol-chitosan powder is taken, the aqueous solution of the glycol-chitosan of 4mg/ml is configured to.
(5) terephthalaldehydic acid-polyethylene glycol powder is taken, terephthalaldehydic acid-polyethylene glycol of 4mg/ml is configured to
Aqueous solution.
(6) dichloromethane solution (the corrosion inhibiter Paeonol of doping 0.001g/ml) of the polycaprolactone of 2.5wt% is prepared,
Obtain hydrophobic material.
(7) modified matrix Mg is soaked in 12h in the ethanol solution of poly-dopamine, and dry, forms transition zone；It soaks again
The 15min in the aqueous solution of glycol-chitosan is steeped, and dry, it is water-soluble to be then soaked in terephthalaldehydic acid-polyethylene glycol
15min in liquid, and it is dry, form reconditioning layer；The anticorrosion material V for being provided only with hydrophilic layer is obtained, Mg-PGD is denoted as.
(8) it will be provided only with the anticorrosion material (Mg-PGD) of hydrophilic layer, be immersed in hydrophobic material, formed hydrophobic
Layer；Anticorrosion material VI is obtained, Mg-PGD-P@PCL is denoted as.
Embodiment 3
The step of embodiment 3 (1)-step (6) is same as Example 2, and embodiment 3 and the difference of embodiment 2 are only that: step
Suddenly the exchange of (7) and step (8) sequence, specifically:
(7) it by modified matrix Mg, is immersed in hydrophobic material, forms hydrophobic layer；It obtains being provided only with hydrophobic layer
Anticorrosion material VII is denoted as Mg-P@PCL.
(8) anticorrosion material for being provided only with hydrophobic layer (Mg-P@PCL) is soaked in the ethanol solution of poly-dopamine
12h, and it is dry, form transition zone；It is soaked in 15min in the aqueous solution of glycol-chitosan again, and dry, is then soaked in pair
15min in aldehyde benzoic acid-polyethylene glycol aqueous solution, and it is dry, form reconditioning layer；Anticorrosion material VIII is obtained, is remembered
Make Mg-P@PCL-PGD, scanning electron microscope (SEM) photograph is as shown in the right side Fig. 3.
Performance test
1, the test of the water retention of matrix Cu and the anticorrosion material I-VI of embodiment 1 and contact angle test
Matrix Cu is taken, the anticorrosion material I (Cu-P@PCL) of hydrophobic layer is provided only with, is provided only with the anticorrosion of hydrophilic layer
Material II (Cu-PGD), anticorrosion material III of the invention (Cu-PGD-P@PCL) and anticorrosion material IV (Cu-P@PCL-
PGD water retention test) is carried out；Specific steps are as follows:
Matrix Cu is taken, the anticorrosion material I (Cu-P@PCL) of hydrophobic layer is provided only with, is provided only with the anticorrosion of hydrophilic layer
Material II (Cu-PGD), anticorrosion material III of the invention (Cu-PGD-P@PCL) and anticorrosion material IV (Cu-P@PCL-
PGD it) is used as sample to be tested, above-mentioned sample is fixed between two syringes using clip, drop is from top to bottom instilled, is seen
Examine the height of water in syringe.It is specific that test result is as follows shown in table 1.
Water droplet is dripped in matrix Cu, the anticorrosion material I (Cu-P@PCL) that is provided only with hydrophobic layer, is provided only with hydrophilic layer
Anticorrosion material II (Cu-PGD) and anticorrosion material III of the invention (Cu-PGD-P@PCL) and anticorrosion material IV (Cu-
P@PCL-PGD) surface, the contact angle of its water is measured, result is as shown in table 1 and Fig. 4.
Table 1
| Test item | Water height/cm | Contact angle/° |
| Cu | 0 | 84.2 |
| Cu-PGD | 0 | 0 |
| Cu-P@PCL | 1.9 | 115.3 |
| Cu-PGD-P@PCL | 2.6 | 109.6 |
| Cu-P@PCL-PGD | 5.1 | 65.1 |
It can be seen from the water retention test result of table 1 matrix Cu (Cu), be provided only with the anticorrosion material of hydrophilic layer
II (Cu-PGD) does not have water retention, and water readily penetrates through；The anticorrosion material I (Cu-P@PCL) for being provided only with hydrophobic layer has
Certain water retention, water are not easy to penetrate；And the water retention of anticorrosion material III (Cu-PGD-P@PCL) of the invention is compared
It is provided only with the anticorrosion material I (Cu-P@PCL) of hydrophobic layer more preferably, but still has water transmission.Anticorrosion material IV of the invention
The water retention of (Cu-P@PCL-PGD) more preferably compared to anticorrosion material III (Cu-PGD-P@PCL), penetrates almost without water.By
This is as it can be seen that excellent using the anti-permeability of anticorrosion material of the invention, and then its Corrosion Protection is excellent.
It is hydrophobic by hydrophobic layer it can be seen from the contact angle test result of table 1 and Fig. 4, and hydrophilic layer is hydrophily
, and can be coated in the surface of matrix copper.
2, the contact angle test on magnesium ingot surface
Water droplet is dripped respectively in matrix Mg (Mg), modified matrix Mg (Mg-H), anticorrosion material V (Mg-PGD), anti-corrosion
Corrosion material VI (Mg-PGD-P@PCL) and anticorrosion material VII (Mg-P@PCL), anticorrosion material VIII (Mg-P@PCL-
PGD the surface of sample to be tested) measures the size of its contact angle, is specifically shown in shown in the following table 2 and Fig. 5.
Table 2
| Test item | Contact angle/° |
| Mg | 56.9 |
| Mg-H | 53.6 |
| Mg-P@PCL | 104.09 |
| Mg-PGD | 28.5 |
| Mg-PGD-P@PCL | 112.49 |
| Mg-P@PCL-PGD | 55.9 |
It is hydrophobic by hydrophobic layer it can be seen from the contact angle test result of table 2 and Fig. 5, and hydrophilic layer is hydrophily
, and can be coated in the surface of matrix magnesium.
3, surface corrosion performance test
Take matrix Mg (Mg), modified matrix Mg (Mg-H), embodiment 2 anticorrosion material V (Mg-PGD), anticorrosion material
Expect anticorrosion material VII (Mg-P@PCL), anticorrosion material VIII (the Mg-P@of VI (Mg-PGD-P@PCL) and embodiment 3
PCL-PGD it) is used as sample to be tested, is immersed in 37 ± 0.5 DEG C of SBF simulated body fluid and is taken after 3 days, 8 days, 12 days, 21 days
It sample and tests its weight-loss ratio out and changes with time, the results are shown in Table 3.
Table 3
| Weight-loss ratio (%) | Mg | Mg-H | Mg-P@PCL | Mg-PGD | Mg-PGD-P@PCL | Mg-P@PCL-PGD |
| 3d | 7.73 | 7.55 | 3.55 | 6.35 | 2.73 | 1.14 |
| 8d | 9.56 | 8.48 | 7.74 | 7.24 | 2.8 | 1.16 |
| 12d | 9.92 | 10.9 | 7.48 | 8.64 | 6.79 | 1.19 |
| 21d | 12.97 | 11.92 | 10.19 | 11.55 | 9.48 | 5.20 |
As can be seen from Table 3, the weight-loss ratio of Mg is only for 7.73%, Mg-PGD-P@PCL weight-loss ratio in 3d in 3d
2.73, and weight-loss ratio when 12d also wants small compared to the initial value of naked magnesium.And the weight-loss ratio of Mg-P@PCL-PGD is only in 3d
1.14% and it is always maintained at the numerical value of very little, weight-loss ratio of the Mg-P@PCL-PGD in 21d also wants small compared to the initial value of naked magnesium.With
Upper result illustrates that water spreads over the surface of anticorrosion material of the invention and will not permeate, and increases the resistance to corrosion of metal.
4, self-healing properties are tested
In the standardized road scratch of surface variations of matrix Mg (Mg) and anticorrosion material VIII (Mg-P@PCL-PGD), then will
It is immersed in 0h, 72h in 37 ± 0.5 DEG C of SBF simulated body fluid, its self-reparing capability of sample observation, knot are taken out after 216h, 468h
Fruit is as illustrated in figures 6-10.
As seen from Figure 6, in 0h, all material is not corroded.
As seen from Figure 7, in 72h, the surface sample Mg starts the Product bulk that is corroded；Anticorrosion material VIII (Mg-
P@PCL-PGD) it is relatively complete.
As seen from Figure 8, in 216h, the surface sample Mg has almost been corroded Product bulk, illustrates do not have completely
Self-reparing capability；Anticorrosion material VIII (Mg-P@PCL-PGD) is still relatively complete.
From Fig. 9 and Figure 10 can be seen that the scratch on the surface anticorrosion material VIII (Mg-P@PCL-PGD) since 72h by
Gradual change is small, has not observed scratch when to 468h, has illustrated that selfreparing has occurred in coating, and the resistance to corrosion on surface is strong.
5, impedance detection
In order to probe into the self-reparing capability of selfreparing composite coating, the present invention is also tested for sample in the impedance of different time
It is worth variation tendency, specifically sample is immersed in SBF simulated body fluid, different number of days or hour take out to survey its impedance spectrum,
The radius of impedance spectrum is bigger, and corrosion resistance is better, as a result as shown in figure 11.
As seen from Figure 11, the impedance value of 0h-60h, naked magnesium are gradually increased, and impedance value reduces after 84h, illustrate that magnesium corrodes
The passivation layer of generation can slow down corrosion, but after passivation layer disappears, corrosion continues to occur.
The impedance value of 0h-36h, Mg-H first increase to be reduced afterwards, shows that passivation layer disappearance post-etching continues to occur.
The impedance value of 0h-36h, Mg-PGD gradually decrease, and start to increase after 108h, and it is blunt to illustrate that corrosion reaction forms
Change layer, reduces corrosion rate；
The impedance value of 0h-84h, Mg-P@PCL reduce, and gradually rise between 84-180h, reduce after 180h, show scratch position
It sets and corrodes, corrode Paeonol in the magnesium ion and hydrophobic layer material of generation and complex reaction occurs form new coating to repair
Damage location has been answered, corrosion is reduced.
The result of Mg-PGD-P@PCL is similar with Mg-P@PCL, illustrates that coating occurs selfreparing and reduces corrosion of metal.
The impedance value of 0-180h, Mg-P@PCL-PGD tend towards stability, and illustrate that influence of the scratch to coating is smaller, hinder after 180h
Anti- value is increased to maximum, and selfreparing, which has occurred, in coating at this time enhances corrosion resistance.
The above embodiment of the present invention be only to clearly illustrate example of the present invention, and not be to the present invention
Embodiment restriction.For those of ordinary skill in the art, it can also make on the basis of the above description
Other various forms of variations or variation.There is no necessity and possibility to exhaust all the enbodiments.It is all of the invention
Made any modifications, equivalent replacements, and improvements etc., should be included in the protection of the claims in the present invention within spirit and principle
Within the scope of.
Claims (12)
1. a kind of application of selfreparing composite coating in anticorrosion, which is characterized in that the selfreparing composite coating includes: phase
The hydrophobic layer and hydrophilic layer of contact, wherein
The hydrophobic layer includes lyophobic dust；
The hydrophilic layer includes reconditioning layer, and the reconditioning layer includes hydroaropic substance A, and the hydroaropic substance A includes dynamic
At least one of state covalent bond.
2. application of the selfreparing composite coating according to claim 1 in anticorrosion, which is characterized in that the hydrophilic layer
It also include the transition zone being in contact with the reconditioning layer；Wherein
The transition zone is present between the reconditioning layer and the hydrophobic layer or the transition zone is present in described review one's lessons by oneself
The side opposite with the hydrophobic layer of cladding；
The transition zone includes hydroaropic substance.
3. application according to claim 1 or 2, which is characterized in that the hydrophobic layer is doped with corrosion inhibiter, it is preferable that institute
State the combination that corrosion inhibiter includes one or more of Paeonol, honey, orange peel and leaf of bamboo.
4. application according to claim 1-3, which is characterized in that the surface of the selfreparing composite coating has
Irregular structure, it is preferable that the irregular structure includes at least one in sunk structure, bulge-structure and reticular structure
Kind.
5. application according to claim 1-4, which is characterized in that the dynamic covalent bond includes amido bond, double
At least one of sulfide linkage, imine linkage and acylhydrazone key.
6. a kind of selfreparing composite coating, which is characterized in that the selfreparing composite coating is any one of claim 1-5 institute
The selfreparing composite coating stated.
7. a kind of anticorrosion material, which is characterized in that the anticorrosion material includes matrix and is formed in described matrix surface
Selfreparing composite coating；The selfreparing composite coating is selfreparing composite coating as claimed in claim 6.
8. anticorrosion material according to claim 7, which is characterized in that the selfreparing composite coating is formed in the base
The surface of body, the hydrophobic layer are in contact with the surface of described matrix, the hydrophilic layer be set to the hydrophobic layer with it is described
The opposite side of matrix；Or
The hydrophilic layer is in contact with the surface of described matrix, the hydrophobic layer be set to the hydrophilic layer with described matrix phase
Anti- side.
9. anticorrosion material according to claim 7 or 8, which is characterized in that described matrix is surface treated matrix；
Preferably, after matrix surface treated, the surface of matrix has reticular structure.
10. a kind of preparation method according to the described in any item anticorrosion materials of claim 7-9 characterized by comprising
Hydroaropic substance A is taken to prepare reconditioning layer material；
Lyophobic dust is taken to prepare hydrophobic material；
The reconditioning layer material and the hydrophobic material is set to be alternatively formed hydrophilic layer and hydrophobic layer on the surface of matrix, it is described
Hydrophilic layer includes reconditioning layer.
11. the preparation method of anticorrosion material according to claim 10, which is characterized in that the preparation method is also wrapped
It includes, hydroaropic substance is taken to prepare buffer layer material；
Transition zone is formed between the reconditioning layer and the hydrophobic layer using the buffer layer material；Or utilize the mistake
It crosses layer material and forms transition zone in the side opposite with the hydrophobic layer of the reconditioning layer.
12. preparation method described in 0 or 11 according to claim 1, which is characterized in that the preparation method further include: to described
Matrix is surface-treated；Preferably, processing is modified using surface of the modifying agent to described matrix；The modifying agent includes
Acid solution；
It is highly preferred that the modifying agent also includes alcohols and/or inorganic salts.
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