CN113914277B - Protective coating for repairing metal surface damage, preparation method and composite material - Google Patents

Protective coating for repairing metal surface damage, preparation method and composite material Download PDF

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Publication number
CN113914277B
CN113914277B CN202111214285.5A CN202111214285A CN113914277B CN 113914277 B CN113914277 B CN 113914277B CN 202111214285 A CN202111214285 A CN 202111214285A CN 113914277 B CN113914277 B CN 113914277B
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fiber cloth
protective coating
layer
resin
curing resin
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CN113914277A (en
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赵文杰
吴英豪
吴杨敏
赵清源
王立平
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Ningbo Institute of Material Technology and Engineering of CAS
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Ningbo Institute of Material Technology and Engineering of CAS
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    • E—FIXED CONSTRUCTIONS
    • E02—HYDRAULIC ENGINEERING; FOUNDATIONS; SOIL SHIFTING
    • E02B—HYDRAULIC ENGINEERING
    • E02B17/00—Artificial islands mounted on piles or like supports, e.g. platforms on raisable legs or offshore constructions; Construction methods therefor
    • E02B17/0017—Means for protecting offshore constructions
    • E02B17/0026—Means for protecting offshore constructions against corrosion
    • 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
    • C09D163/10—Epoxy resins modified by unsaturated compounds
    • 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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    • C09D167/00—Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers
    • C09D167/06—Unsaturated polyesters having carbon-to-carbon unsaturation
    • 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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    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • 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
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
    • E—FIXED CONSTRUCTIONS
    • E02—HYDRAULIC ENGINEERING; FOUNDATIONS; SOIL SHIFTING
    • E02D—FOUNDATIONS; EXCAVATIONS; EMBANKMENTS; UNDERGROUND OR UNDERWATER STRUCTURES
    • E02D27/00—Foundations as substructures
    • E02D27/32—Foundations for special purposes
    • E02D27/52—Submerged foundations, i.e. submerged in open water
    • E—FIXED CONSTRUCTIONS
    • E02—HYDRAULIC ENGINEERING; FOUNDATIONS; SOIL SHIFTING
    • E02D—FOUNDATIONS; EXCAVATIONS; EMBANKMENTS; UNDERGROUND OR UNDERWATER STRUCTURES
    • E02D31/00—Protective arrangements for foundations or foundation structures; Ground foundation measures for protecting the soil or the subsoil water, e.g. preventing or counteracting oil pollution
    • E02D31/06—Protective arrangements for foundations or foundation structures; Ground foundation measures for protecting the soil or the subsoil water, e.g. preventing or counteracting oil pollution against corrosion by soil or water
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C08K2003/382—Boron-containing compounds and nitrogen
    • C08K2003/385—Binary compounds of nitrogen with boron
    • 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
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Abstract

The invention provides a protective coating for repairing metal surface damage, a preparation method and a composite material. The protective coating is arranged on the surface of a damaged area of a metal material matrix and comprises a resin material layer, a fiber cloth layer and a rapid curing resin layer which are sequentially arranged on the surface of the damaged area of the metal material matrix from inside to outside, wherein the fiber cloth layer comprises fiber cloth subjected to surface modification, the rapid curing resin layer comprises a photosensitizer or a photoinitiator, and the rapid curing resin layer further comprises a photo-curing resin and a functional nano material modified by covalent bonds or non-covalent bonds. The protective coating has higher anti-erosion abrasion and anti-corrosion effects, and the interface performance among layers of the protective coating is improved by adding the modified functional nano material into the fast-curing resin and modifying the fiber cloth, so that the protective coating can resist the damages of corrosion, external impact, erosion and the like on the surface of a metal material matrix in the ocean harsh environment.

Description

Protective coating for repairing metal surface damage, preparation method and composite material
Technical Field
The invention relates to the technical field of composite materials, in particular to a protective coating for repairing metal surface damage, a preparation method and a composite material.
Background
Under the harsh environment of ocean, various ocean engineering materials are in the ocean environment with high temperature, high humidity and high salt mist for a long time, and particularly under the continuous erosion of the spray, the erosion and abrasion of the seawater and the sediment in the tidal range area and the corrosion action, the accelerated damage failure of the metal materials is easy to cause. In addition, once corrosion damage occurs on the surfaces of steel pipe piles and the like, more serious corrosion damage is caused under the alternating coupling action of the severe environmental conditions, so that the service life of the bridge is greatly reduced, great hidden danger is caused to the life safety of people, and serious economic loss is caused.
Disclosure of Invention
The invention solves the problems that steel pipe piles and the like in seawater are easy to be corroded and damaged by the influence of ocean severe environment, potential safety hazards exist, and the service life of the steel pipe piles is reduced.
In order to solve the problems, the invention provides a protective coating for repairing metal surface damage, which is arranged on the surface of a damaged area of a metal material matrix and comprises a resin material layer, a fiber cloth layer and a rapid-curing resin layer which are sequentially arranged on the surface of the damaged area of the metal material matrix from inside to outside, wherein the fiber cloth layer comprises a fiber cloth subjected to surface modification, the rapid-curing resin layer comprises a photosensitizer or a photoinitiator, and the rapid-curing resin layer further comprises a photo-curing resin and a functional nano material modified by covalent bonds or non-covalent bonds.
Preferably, the addition amount of the functional nano material modified by covalent bond or non-covalent bond is 0.5wt% to 5wt%, and the content of the photosensitizer or the photoinitiator is 6wt% to 10wt%.
Preferably, the fiber cloth comprises at least one of ultra-high molecular weight polyether-ether-ketone fibers, nanocellulose fibers, carbon nanotube fibers, titanium carbide nanofibers and fluorocarbon fibers.
Preferably, the functional nanomaterial comprises one of a two-dimensional platelet material, a nanoparticle, and a rod-shaped nanomaterial.
Preferably, the functional nanomaterial comprises one of titanium carbide, graphite phase carbon nitride, fluorinated graphene particles, spherical boron nitride particles, niobium carbide, and lamellar ultra-high molecular weight polyethylene.
The invention also provides a preparation method of the protective coating, which is used for preparing the protective coating for repairing the damage of the metal surface and comprises the following steps:
coating a resin material to the damaged area of the metal material matrix, and preparing a resin material layer on the surface of the damaged area of the metal material matrix;
the fiber cloth is stuck to the resin material layer after being subjected to surface modification, and a fiber cloth layer is formed on the surface of the resin material layer;
adding a photosensitizer or a photoinitiator into the photo-curing resin, uniformly mixing, modifying the functional nano material to obtain a covalent bond modified or non-covalent bond modified functional nano material, adding the covalent bond modified or non-covalent bond modified functional nano material into the photo-curing resin to obtain photo-curing composite resin, coating the photo-curing composite resin onto the fiber cloth layer, and forming a rapid curing resin layer on the surface of the fiber cloth layer;
and (3) irradiating the fast-curing resin layer for a set time by adopting sunlight or ultraviolet band light rays to obtain the protective coating for repairing the damage of the metal surface.
Preferably, the surface modification method of the fiber cloth comprises the following steps: the fiber cloth is subjected to surface functionalization treatment, and then the functionalized polymer is grafted on the surface of the fiber cloth after the functionalization treatment.
Preferably, the modification treatment process of the functional nanomaterial comprises the following steps: firstly, carrying out multi-surface modification on the functional nano material, and then carrying out multi-scale interface regulation and control treatment.
Preferably, when the protective coating for repairing the damage of the metal surface is irradiated by sunlight, the set time is 1h-2h;
when the ultraviolet band light is adopted to irradiate the protective coating for repairing the damage of the metal surface, the wavelength range of the ultraviolet band light is 330nm-405nm, and the set time is less than or equal to 10min.
The invention also provides a composite material, which comprises a metal material matrix and the protective coating for repairing the damage of the metal surface, or the protective coating for repairing the damage of the metal surface, which is prepared by the preparation method of the protective coating.
Compared with the prior art, the protective coating for repairing the metal surface damage and the coating preparation method provided by the invention have the following beneficial effects:
according to the protective coating, the bottom resin is coated on the damaged surface of the metal material matrix, the interface performance between the fiber cloth layer and the two resins of the bottom layer and the surface layer is improved through surface modification of the middle fiber cloth layer, the surface layer resin is the rapid curing resin reinforced by the nano material, and the interface performance between the nano material and the rapid curing resin is greatly improved after the nano material is modified, so that the nano material and the fiber reinforced composite material are prepared. The composite material has higher impact resistance and toughness, can quickly repair the damage on the surface of the steel pipe pile, resists corrosion damage caused by the marine environment with high humidity, high heat and high salt mist in the later service process of the steel pipe pile, and resists impact damage caused by the beating of sea waves and the erosion of sediment in a spray splash zone.
The protective coating prepared by the method has higher anti-erosion and anti-abrasion effects and anti-corrosion protective effects. By adding the modified functional nano material into the fast-curing resin and modifying the fiber cloth, the interface performance (interface compatibility and interface shear strength) among the layers of the protective coating is improved, so that the protective coating can resist the damages of corrosion, impact, erosion and the like on the surface of the metal material matrix in the ocean harsh environment.
Drawings
FIG. 1 is a flowchart of a method for preparing a protective coating according to an embodiment of the present invention;
FIG. 2 is a surface photomicrograph of the protective coating of example 1 of the present invention;
FIG. 3 is a surface topography of the protective coating produced in example 1 of the present invention after erosive wear;
FIG. 4 is a graph showing the electrochemical impedance of the protective coating prepared in example 1 of the present invention.
Detailed Description
Under the ocean harsh environment, the metal material is extremely easily damaged, and comprises the thickness reduction of the metal material caused by local corrosion pits, corrosion perforation, uniform corrosion and the like caused by the ocean high-humidity high-heat high-salt spray environment, the quality loss of the metal surface caused by scratch, scratch and the like, and the damage caused by erosion and abrasion and the like caused by sea wave beating, sediment erosion and the like, wherein the damage of the metal material is usually repaired in the form of fiber prepreg in the prior art, such as the steel pipe pile and the like is subjected to erosion corrosion for a long time, and the repair mode can not meet the long-service safety requirements of the material in the ocean harsh environment, especially in the splash zone of the wave. Therefore, the invention provides the protective coating for repairing the metal surface damage and the preparation method of the protective coating, and provides a new thought for preparing the coating for repairing the metal material corrosion damage.
In order that the above objects, features and advantages of the invention will be readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings.
The embodiment of the invention provides a protective coating (hereinafter referred to as protective coating) for repairing metal surface damage, which is arranged on the surface of a metal material matrix damage area and comprises a resin material layer (also called inner layer resin or bottom layer resin), a fiber cloth layer and a rapid-curing resin layer (also called outer layer resin or surface layer resin) which are sequentially arranged on the surface of the metal material matrix damage area from inside to outside, wherein the fiber cloth layer comprises fiber cloth subjected to surface modification, the rapid-curing resin layer comprises a photosensitizer or a photoinitiator, and the rapid-curing resin layer further comprises a photo-curing resin and a functional nano material modified by covalent bonds or non-covalent bonds.
The resin material layer is used as inner resin, is mainly used for bonding a composite coating formed by outer resin and fiber cloth to the surface of a metal matrix, and the fiber cloth layer is used as an intermediate layer, and is fiber cloth subjected to surface modification, and the interfacial compatibility and interfacial shear strength between the fiber cloth and the inner and outer resin can be improved through surface modification, so that the fiber cloth, the resin material layer and the fast-curing resin layer have excellent interfacial properties, and the overall corrosion resistance and impact resistance of the protective coating are improved.
According to the embodiment, the protective coating is arranged on the surface of the corrosion damage area of the metal material matrix such as the steel pipe pile, the composite coating with the supporting structure is obtained by utilizing the obdurability of the fiber cloth, the functional nano material is added into the fast curing resin, and is the nano material modified by covalent bonds and non-covalent bonds, so that the functional nano material and the fast curing resin have good interface compatibility, higher interface shear strength and other interface performances, and in the corrosion process of the metal material matrix, the nano material can resist the expansion of cracks generated by external force in the protrusion, so that the interface between the nano material and the fast curing resin is perfect and no crack is generated, the impact resistance and toughness of the outer layer fast curing resin are increased, and the composite coating system with excellent anti-corrosion abrasion and corrosion protection effects is obtained.
Therefore, the protective coating of the embodiment is formed by modifying the surface of the fiber cloth and coating the surface of the fiber cloth with the rapid curing resin added with the modified nano material, and the addition of the nano material prevents the outer layer resin from being cracked due to external force beating or impact and the like, so that the toughness and the anti-beating capability of the outer layer resin are improved. In addition, the nano material is further modified, so that the nano material has good dispersibility in the fast-curing resin, the interface performance between the nano material and the fast-curing resin is improved after the fast-curing resin is cured, the interface compatibility and the interface shear strength of the nano material and the fast-curing resin are improved, and the impact shear capacity of the outer layer resin is further improved, so that the nano material and the fiber-reinforced composite material system is obtained. The composite material can quickly repair the damage on the surface of the steel pipe pile, can resist corrosion damage caused by the marine environment with high humidity, high heat and high salt mist in the later service process of the steel pipe pile, and can resist impact damage caused by the beating of sea waves and the erosion of silt in a spray splash zone, so that the protective coating has higher erosion and wear resistance effect and corrosion resistance effect.
In some embodiments, the functional nanomaterial modified by covalent bond or non-covalent bond in the outer resin is added in an amount of 0.5wt% to 5wt%, the content of the photosensitizer or photoinitiator is 6wt% to 10wt%, and the rest is the fast-curing resin, wherein the wt% represents mass percent. Illustratively, the fast curing resin may be an epoxy acrylate, a urethane acrylate, a polyester acrylate, or the like.
The fiber cloth comprises at least one of ultra-high molecular weight polyether-ether-ketone fibers, nanocellulose fibers, carbon nanotube fibers, titanium carbide nanofibers and fluorocarbon fibers. The fiber cloth comprises different textile forms and can be obtained by blending two or more fibers. The fiber can comprise organic fiber, inorganic fiber or composite of organic fiber and inorganic fiber, and the blend fiber can be obtained by compositing two fibers or compositing a plurality of fibers.
The functional nanomaterial includes one of a two-dimensional platelet material, a nanoparticle, and a rod-shaped nanomaterial. Illustratively, the functional nanomaterial may be one of titanium carbide, graphite phase carbon nitride, fluorinated graphene particles, spherical boron nitride particles, niobium carbide, and lamellar ultra-high molecular weight polyethylene.
As shown in fig. 1, another embodiment of the present invention provides a method for preparing the protective coating, including the steps of:
coating a resin material to a damaged area of a metal material matrix, and preparing a resin material layer on the surface of the damaged area of the metal material matrix;
the fiber cloth is stuck to the resin material layer after surface modification, and a fiber cloth layer is formed on the surface of the resin material layer;
adding a photosensitizer or a photoinitiator into the photo-curing resin, uniformly mixing, modifying the functional nano material to obtain a covalent bond modified or non-covalent bond modified functional nano material, adding the covalent bond modified or non-covalent bond modified functional nano material into the photo-curing resin to obtain photo-curing composite resin, coating the photo-curing composite resin on a fiber cloth layer, and forming a rapid curing resin layer on the surface of the fiber cloth layer;
and (3) irradiating the fast-curing resin layer for a set time by adopting sunlight or ultraviolet band rays to obtain the protective coating for repairing the damage of the metal surface.
The protective coating of the embodiment can be rapidly cured under the irradiation of ultraviolet band light or sunlight, wherein the wavelength range of the ultraviolet band light is 330nm-405nm. When the protective coating for repairing the damage of the metal surface is irradiated by sunlight, the time is set to be 1h-2h, preferably 2h; when ultraviolet band light is adopted to irradiate the protective coating for repairing the damage of the metal surface, the set time is less than or equal to 10min.
In addition, the protective coating of the embodiment enhances the mechanical property, the erosion abrasion resistance and the corrosion resistance of the fast-curing resin by adding the functional nano material into the fast-curing resin, so as to meet the requirement of long-life safe service of metal material matrixes such as steel pipe piles and the like in a marine harsh environment.
The modification of the functional nanomaterial may be covalent bond modification or non-covalent bond modification, for example, covalent bond modification is performed on the ultra-high molecular weight polyethylene nanomaterial by chitosan, or modification is performed on the surface of graphene by supermolecule effects such as pi-pi interaction, ionic bond, hydrogen bond and the like.
Wherein, the surface modification method of the fiber cloth comprises the following steps: the fiber cloth is subjected to surface functionalization treatment, and then the functionalized polymer is grafted on the surface of the fiber cloth after the functionalization treatment. Illustratively, the fiber cloth is subjected to acid-base oxidation treatment so that oxygen-containing functional groups, including carboxyl groups, amino groups, hydroxyl groups and the like, are obtained on the surface of the fiber cloth, and polydopamine, sulfonated chitosan, catecholamine, fluorine-containing thiol and the like are grafted on the surface of the functionalized fiber cloth, so that the interfacial compatibility and the interlaminar shear strength between the fiber cloth and the resin are improved.
Wherein, the modification treatment process of the functional nano material comprises the following steps: the functional nanomaterial is first surface modified, for example, the functional nanomaterial is surface functionalized, including fluorination, surfactant treatment, grafting of low surface energy species, and the like. And then carrying out multi-scale interface regulation and control treatment on the functional nano material with the modified surface, and obtaining the composite material with different functionalities by regulating and controlling the content, the combination form and the distribution state of the nano material, thereby increasing the dispersibility of the nano material in the resin, improving the compatibility of the nano material and the resin and the interface shear strength, and further improving the mechanical property and the erosion and abrasion resistance of the composite material.
The invention also provides a composite material, which comprises a metal material matrix and a protective coating for repairing damage on the metal surface, wherein the protective coating can be obtained by adopting the preparation method. Wherein the damage to the surface of the metallic material substrate comprises corrosion damage and/or impact damage.
The present invention will be described in detail with reference to the following examples.
Example 1
Adding a cationic photoinitiating material into epoxy acrylate, and uniformly mixing, wherein the content of the photoinitiating material is 5wt%;
covalent bond modification is carried out on the ultra-high molecular weight polyethylene nano material by adopting chitosan, and the ultra-high molecular weight polyethylene nano material with the mass fraction of 1wt% after the covalent bond modification is added into epoxy acrylate to obtain the epoxy acrylic composite resin coating;
coating epoxy resin on the surface of the corrosion damaged steel pipe pile, and sticking the surface-modified plain ultra-high molecular weight polyphenylene sulfide fiber cloth to the epoxy resin;
coating the epoxy acrylic composite resin coating on the surface of the ultra-high molecular weight polyphenylene sulfide fiber cloth to form a rapid curing fiber cloth reinforced coating shown in figure 2;
at normal temperature, the rapidly cured fiber cloth reinforcement coating is fully cured after two hours of irradiation under sunlight, forming a hard fiber cloth coating, i.e. the protective coating mentioned above.
As shown in fig. 2, which is a surface optical photograph of the rapid-curing fiber cloth reinforced coating prepared in this example, it can be seen from fig. 2 that the rapid-curing fiber cloth reinforced coating is well bonded, and no bubbling, separation, etc. occur, which indicates that the interfaces of the bottom resin (i.e., the inner resin material layer), the fiber cloth, and the surface nano-material reinforced rapid-curing resin (i.e., the outer rapid-curing resin layer) are well bonded. Therefore, the method of the embodiment can quickly repair the damage of the surface of the metal material, and form the anti-corrosion coating with high surface quality, thereby having good effects of resisting erosive wear and corrosion protection and good appearance. In addition, the nano material reinforced fast-curing resin has smooth surface and no pore crack, which lays a good foundation for the erosion abrasion resistance and corrosion protection of the protective coating in the subsequent service process.
As shown in fig. 3, fig. 3 is an optical photograph of the etched surface of the protective coating layer prepared in this example after the surface is etched in a silicon carbide aqueous solution (silicon carbide mass fraction 20 wt%) at a speed of 7m/s for 1 hour, and as can be seen from fig. 3, the nano-material reinforced rapid-curing resin has small surface etching spots, and after the etching, the volume loss and the mass loss are small, and can resist the impact of high-strength sand water flow, which indicates that the nano-material reinforced rapid-curing resin has excellent resistance to long-time erosion and abrasion, and exhibits long-life safety service performance. Therefore, the toughness and the impact resistance of the fast curing resin can be improved after the functional nano material ultra-high molecular weight polyethylene is added into the fast curing resin, and the functional nano material ultra-high molecular weight polyethylene is mainly due to the good dispersibility of the ultra-high molecular weight polyethylene nano material in the fast curing resin, so that the interface performance between the resin cured ultra-high molecular weight polyethylene nano material and the fast curing resin is greatly improved, wherein the interface performance comprises interface compatibility and interface shear strength.
As shown in fig. 4, fig. 4 is an electrical impedance curve of the protective coating (the fiber cloth coating shown in the drawing) prepared in this example, in which the abscissa represents Frequency (Frequency) in Hertz (HZ), the ordinate represents impedance in Ohm (Ohm), and the Frequency and the impedance are expressed in logarithmic form. As can be seen from FIG. 4, the fiber cloth coating in this embodiment has a relatively high impedance modulus, and its low frequency impedance value can reach 4×10 11 Ω/cm 2 And has excellent erosion resistance. For the anti-corrosion coating, the nano material reinforced fast-curing resin has excellent anti-corrosion medium permeation effect, and the anti-corrosion coating can improve the corrosion protection performance of the fast-curing resin in the subsequent process.
Example 2
Adding a photosensitizer into polyurethane acrylic ester, and uniformly mixing, wherein the content of the photosensitizer is 8wt%, and adding 1wt% of boron nitride nanomaterial modified by nanocellulose covalent bonds into the polyurethane acrylic ester to obtain polyurethane acrylic ester composite resin coating;
sticking twill aramid fiber cloth to the surface of the epoxy resin coated corrosion damaged steel pipe pile;
coating polyurethane acrylate composite resin paint on the surface of the twill aramid fiber cloth to form a fiber cloth composite material;
at normal temperature, the fast curing fiber cloth reinforced coating is completely cured to form a hard fiber cloth coating after being irradiated by ultraviolet light with 365nm wave band for 2 minutes.
The fiber cloth coating in this embodiment has a high impedance modulus, and its low frequency impedance value can reach 8×10 11 Ω/cm 2 And has excellent erosion resistance.
Example 3
Adding a photosensitizer into polyester acrylic ester, and uniformly mixing, wherein the content of the photosensitizer is 6wt%, and adding 1wt% of titanium carbide nano material modified by fluorosilane covalent bonds into the polyurethane acrylic ester to obtain polyester acrylic ester composite resin coating;
adhering fiber cloth blended by glass fibers and carbon fibers to the surface of the corrosion damaged steel pipe pile coated by epoxy resin;
coating polyester acrylate composite resin paint on the surface of fiber cloth blended by glass fibers and carbon fibers to form a fiber cloth composite material;
at normal temperature, the fast curing fiber cloth reinforced coating is completely cured to form a hard fiber cloth coating after being irradiated by ultraviolet light with the wavelength of 395nm for 8 minutes.
The low frequency impedance value of the fiber cloth coating in the embodiment can reach 5 multiplied by 10 11 Ω/cm 2 And has excellent erosion resistance.
Example 4
Adding a photoinitiation material into epoxy acrylate, and uniformly mixing, wherein the content of the photoinitiation material is 6wt%, and adding 1wt% of fluorinated graphene nano material modified by chitosan covalent bonds into the epoxy acrylate to obtain an epoxy acrylate resin composite coating;
pasting fiber cloth blended by carbon fibers and aramid fibers on the surface of the steel pipe pile with the epoxy resin coated on the corrosion damage;
coating the epoxy acrylate resin composite coating on the surface of fiber cloth blended by carbon fibers and aramid fibers to form a plain fiber cloth composite material;
at normal temperature, the fast curing fiber cloth reinforced coating is completely cured to form a hard fiber cloth coating after being irradiated by ultraviolet light in the 330nm wave band for 3 minutes.
The low frequency impedance value of the fiber cloth coating in the embodiment can reach 7.5 multiplied by 10 11 Ω/cm 2 And has excellent erosion resistance.
Example 5
Adding a photoinitiation material into epoxy acrylate, and uniformly mixing, wherein the content of the photoinitiation material is 10wt%, and adding 5wt% of fluorinated graphene nano material modified by chitosan covalent bonds into the epoxy acrylate to obtain an epoxy acrylate resin composite coating;
pasting fiber cloth blended by carbon fibers and aramid fibers on the surface of the steel pipe pile with the epoxy resin coated on the corrosion damage;
coating the epoxy acrylate resin composite coating on the surface of fiber cloth blended by carbon fibers and aramid fibers to form a plain fiber cloth composite material;
at normal temperature, the fast curing fiber cloth reinforced coating is completely cured to form a hard fiber cloth coating after being irradiated by ultraviolet light in the 330nm wave band for 5 minutes.
The low frequency impedance value of the fiber cloth coating in the embodiment can reach 8.0 multiplied by 10 11 Ω/cm 2 And has excellent erosion resistance.
Example 6
Adding a photoinitiation material into epoxy acrylate, and uniformly mixing, wherein the content of the photoinitiation material is 6wt%, and adding 0.5wt% of fluorinated graphene nano material modified by chitosan covalent bonds into the epoxy acrylate to obtain an epoxy acrylate resin composite coating;
pasting fiber cloth blended by carbon fibers and aramid fibers on the surface of the steel pipe pile with the epoxy resin coated on the corrosion damage;
coating the epoxy acrylate resin composite coating on the surface of fiber cloth blended by carbon fibers and aramid fibers to form a plain fiber cloth composite material;
at normal temperature, the fast curing fiber cloth reinforced coating is completely cured to form a hard fiber cloth coating after being irradiated by ultraviolet light in the 330nm wave band for 10 minutes.
The low frequency impedance value of the fiber cloth coating in the embodiment can reach 6.0 multiplied by 10 11 Ω/cm 2 And has excellent erosion resistance.
Although the present disclosure is described above, the scope of protection of the present disclosure is not limited thereto. Various changes and modifications may be made by one skilled in the art without departing from the spirit and scope of the disclosure, and these changes and modifications will fall within the scope of the invention.

Claims (7)

1. The protective coating for repairing the metal surface damage is characterized by comprising a resin material layer, a fiber cloth layer and a rapid curing resin layer, wherein the resin material layer, the fiber cloth layer and the rapid curing resin layer are sequentially arranged on the surface of a metal material substrate damage area from inside to outside, the resin material layer is epoxy resin, the fiber cloth layer comprises fiber cloth subjected to surface modification, the fiber cloth subjected to surface modification is obtained by grafting a functionalized polymer after carrying out functionalization treatment on the surface of the fiber cloth, the rapid curing resin layer comprises a photosensitizer or a photoinitiator, the rapid curing resin layer also comprises a photo-curing resin and a covalent bond or non-covalent bond modified functional nanomaterial, the photo-curing resin comprises epoxy acrylate, polyurethane acrylate or polyester acrylate, the functional nanomaterial comprises one of titanium carbide, graphite phase carbon nitride, fluorinated graphene, spherical boron nitride, niobium carbide and ultrahigh molecular weight polyethylene, the covalent bond or non-covalent bond modified functional nanomaterial comprises a nanomaterial obtained by covalent modification of the ultrahigh molecular weight polyethylene with chitosan, and the covalent bond modified nanomaterial obtained by covalent bond modification of the spherical boron nitride with the spherical boron nitride or the covalent bond modified nanomaterial obtained by covalent bond modification of the fluorinated silane with the spherical boron nitride.
2. The protective coating for repairing damaged metal surfaces according to claim 1, wherein the functional nanomaterial modified by covalent or non-covalent bonds is added in an amount of 0.5wt% to 5wt%, and the photosensitizer or photoinitiator is contained in an amount of 6wt% to 10wt%.
3. The protective coating for repairing metal surface damage of claim 1, wherein the fiber cloth comprises at least one of ultra-high molecular weight polyetheretherketone fibers, nanocellulose fibers, carbon nanotube fibers, titanium carbide nanofibers, and fluorocarbon fibers.
4. A method for preparing a protective coating for repairing damage to a metal surface according to any one of claims 1 to 3, comprising:
coating a resin material to the damaged area of the metal material matrix, and preparing a resin material layer on the surface of the damaged area of the metal material matrix;
the fiber cloth is stuck to the resin material layer after being subjected to surface modification, and a fiber cloth layer is formed on the surface of the resin material layer;
adding a photosensitizer or a photoinitiator into the photo-curing resin, uniformly mixing, modifying the functional nano material to obtain a covalent bond modified or non-covalent bond modified functional nano material, adding the covalent bond modified or non-covalent bond modified functional nano material into the photo-curing resin to obtain photo-curing composite resin, coating the photo-curing composite resin onto the fiber cloth layer, and forming a rapid curing resin layer on the surface of the fiber cloth layer;
and (3) irradiating the fast-curing resin layer for a set time by adopting sunlight or ultraviolet band light rays to obtain the protective coating for repairing the damage of the metal surface.
5. The method for preparing the protective coating according to claim 4, wherein the modification treatment process of the functional nanomaterial comprises: firstly, carrying out multi-surface modification on the functional nano material, and then carrying out multi-scale interface regulation and control treatment.
6. The method for producing a protective coating according to claim 4, wherein the set time is 1h to 2h when the protective coating for repairing a damaged metal surface is irradiated with solar light;
when the ultraviolet band light is adopted to irradiate the protective coating for repairing the damage of the metal surface, the wavelength range of the ultraviolet band light is 330nm-405nm, and the set time is less than or equal to 10min.
7. A composite material comprising a metal material matrix and a protective coating for repairing a metal surface damage according to any one of claims 1 to 3 or a protective coating for repairing a metal surface damage produced by the method of producing a protective coating according to any one of claims 4 to 6.
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