CN113914277A - 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
CN113914277A
CN113914277A CN202111214285.5A CN202111214285A CN113914277A CN 113914277 A CN113914277 A CN 113914277A CN 202111214285 A CN202111214285 A CN 202111214285A CN 113914277 A CN113914277 A CN 113914277A
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protective coating
fiber cloth
resin
layer
damage
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CN202111214285.5A
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CN113914277B (en
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赵文杰
吴英豪
吴杨敏
赵清源
***
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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
    • 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
    • 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
    • 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
    • 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
    • C08K2201/011—Nanostructured additives

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 the metal material matrix and comprises a resin material layer, a fiber cloth layer and a rapid curing resin layer which are sequentially arranged from inside to outside on the surface of the damaged area of the metal material matrix, 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 photocuring resin and a functional nano material modified by a covalent bond or a non-covalent bond. The protective coating has higher erosion, abrasion and corrosion resistant effects, and the interface performance between layers of the protective coating is improved by adding the modified functional nano material into the fast curing resin and performing modification treatment on the fiber cloth, so that the protective coating can resist damages such as corrosion, external force impact, erosion and the like to the surface of the metal material matrix in a severe marine 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 severe ocean environments, various ocean engineering materials are in high-temperature, high-humidity and high-salt-mist ocean environments for a long time, and especially under the actions of continuous wave erosion, erosion abrasion and corrosion of seawater and silt in a tidal range, accelerated damage and failure of metal materials are easily caused. In addition, once the surfaces of the steel pipe piles and the like are corroded and damaged, more serious corrosion damage is caused under the alternating coupling action of the harsh environment conditions, so that the service life of the bridge is greatly shortened, great hidden dangers are caused to the life safety of people, and serious economic loss is caused.
Disclosure of Invention
The invention solves the problems that the steel pipe pile in seawater and the like are easily influenced by the severe ocean environment to cause corrosion damage, have potential safety hazard and reduce the service life of the steel pipe pile.
In order to solve the above problems, the present invention provides a protective coating for repairing metal surface damage, which is disposed on the surface of a damaged area of a metal material substrate, and comprises a resin material layer, a fiber cloth layer and a fast curing resin layer, which are sequentially disposed on the surface of the damaged area of the metal material substrate from inside to outside, wherein the fiber cloth layer comprises a fiber cloth with a modified surface, the fast curing resin layer comprises a photosensitizer or a photoinitiator, and the fast curing resin layer further comprises a photo-curing resin and a functional nanomaterial modified by a covalent bond or a non-covalent bond.
Preferably, the addition amount of the covalent bond or non-covalent bond modified functional nano material is 0.5 wt% to 5 wt%, and the content of the photosensitizer or the photoinitiator is 6 wt% to 10 wt%.
Preferably, the fiber cloth comprises at least one of ultra-high molecular weight polyether ether ketone fibers, nano cellulose fibers, carbon nanotube fibers, titanium carbide nano fibers and fluorocarbon fibers.
Preferably, the functional nanomaterial comprises one of a two-dimensional sheet material, a nanoparticle, and a rod-like nanomaterial.
Preferably, the functional nanomaterial comprises one of titanium carbide, graphite-phase carbon nitride, fluorinated graphene particles, spherical boron nitride particles, niobium carbide, and flake 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 on the damaged area of the metal material substrate, and preparing a resin material layer on the surface of the damaged area of the metal material substrate;
carrying out surface modification on fiber cloth, then adhering the fiber cloth to the resin material layer, and forming a fiber cloth layer on the surface of the resin material layer;
adding a photosensitizer or a photoinitiator into a photocuring resin, uniformly mixing, carrying out modification treatment on a functional nano material to obtain a covalent bond or non-covalent bond modified functional nano material, adding the covalent bond or non-covalent bond modified functional nano material into the photocuring resin to obtain a photocuring composite resin, coating the photocuring composite resin on the fiber cloth layer, and forming a quick curing resin layer on the surface of the fiber cloth layer;
and irradiating the rapid curing resin layer for a set time by adopting sunlight or ultraviolet band light to prepare 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 firstly subjected to surface functionalization treatment, and then functionalized macromolecules are grafted on the surface of the fiber cloth after the functionalization treatment.
Preferably, the modification treatment process of the functional nano material comprises the following steps: firstly, performing multi-surface modification on the functional nano material, and then performing 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-2 h;
when the protective coating for repairing the metal surface damage is irradiated by ultraviolet band light, the wavelength range of the ultraviolet band light is 330nm-405nm, and the set time is less than or equal to 10 min.
The invention also provides a composite material, which comprises a metal material substrate and the protective coating for repairing the metal surface damage, or the protective coating for repairing the metal surface damage, which is prepared by the preparation method of the protective coating.
Compared with the prior art, the protective coating for repairing metal surface damage and the preparation method of the coating 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 middle fiber cloth layer is subjected to surface modification to improve the interface performance between the fiber cloth layer and the bottom and surface resins, the surface resin is a nano material reinforced fast curing resin, and the nano material is modified to greatly improve the interface performance between the nano material and the fast curing resin, so that the nano material and fiber reinforced composite material is prepared. The composite material has higher shock resistance and toughness, can quickly repair the damage on the surface of the steel pipe pile, resists the 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 the impact damage caused by the beating of sea waves and the erosion of silt in a spray splashing area.
The protective coating prepared by the method has higher erosion and abrasion resistance and corrosion resistance protection effect. By adding the modified functional nano material into the fast curing resin and carrying out modification treatment on the fiber cloth, the interface performance (interface compatibility and interface shear strength) among all layers of the protective coating is improved, so that the protective coating can resist the damages such as corrosion, impact, erosion and the like to the surface of the metal material matrix in a marine severe environment.
Drawings
FIG. 1 is a flow chart of a method for preparing a protective coating in an embodiment of the invention;
FIG. 2 is an optical photograph of the surface of a protective coating made in example 1 of the present invention;
FIG. 3 is a surface topography map of the protective coating made in example 1 of the present invention after erosive wear;
FIG. 4 is a graph of the electrochemical impedance of the protective coating made in example 1 of the present invention.
Detailed Description
In a severe ocean environment, a metal material is extremely easy to damage, and comprises a metal material thickness reduction caused by local corrosion pitting, corrosion perforation, uniform corrosion and the like in a high-humidity high-heat high-salt mist ocean environment, quality loss of a metal surface caused by scratching, scratching and the like, erosion abrasion and other damages caused by sea wave beating, silt erosion and the like. Therefore, the protective coating for repairing metal surface damage and the preparation method thereof provided by the invention provide a new idea for preparing the coating for repairing metal material corrosion damage.
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in detail below.
The embodiment of the invention provides a protective coating (hereinafter referred to as a protective coating) for repairing metal surface damage, which is arranged on the surface of a damaged area of a metal material substrate 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), wherein the resin material layer is arranged on the surface of the damaged area of the metal material substrate from inside to outside in sequence, the fiber cloth layer comprises fiber cloth subjected to surface modification, the rapid curing resin layer comprises a photosensitizer or photoinitiator, and the rapid curing resin layer also comprises photocuring resin and a functional nano material modified by covalent bonds or non-covalent bonds.
The resin material layer is used as inner layer resin and mainly used for bonding a composite coating formed by outer layer resin and fiber cloth to the surface of a metal matrix, the fiber cloth layer is used as a middle layer and is the fiber cloth subjected to surface modification, and the interface compatibility and the interface shear strength between the fiber cloth and the inner and outer layer resin can be improved through the surface modification, so that the fiber cloth, the resin material layer and the rapid curing resin layer have excellent interface performance, and the overall corrosion resistance and the impact resistance of the protective coating are improved.
In 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, functional nano materials are added into the fast curing resin, and the functional nano materials are nano materials modified by covalent bonds and non-covalent bonds, therefore, the functional nano material and the fast curing resin have good interface compatibility, higher interface shear strength and other interface properties, in the process of corroding the metal material substrate, the nano materials can resist the expansion of cracks in the protrusions caused by external force, the interface between the nano material and the fast curing resin is intact and no crack is generated, and the shock resistance and the toughness of the outer layer fast curing resin are improved, so that the composite coating system with excellent erosion wear resistance and corrosion protection effects is obtained.
From this, the protective coating of this embodiment is through to fibre cloth surface modification to and at fibre cloth surface coating the fast curing resin that has added modified nano-material, because the addition of nano-material, avoid outer resin to receive the crackle that external force patted or assaulted etc. and produced, improved the toughness and the anti-impact ability of outer resin. And 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 between the nano material and the fast curing resin are improved, the impact shear resistance of the outer layer resin is further improved, and the nano material and 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 fog in the later service process of the steel pipe pile, and can resist impact damage caused by flapping of sea waves and erosion of silt in a spray splashing area, so that the protective coating has higher erosion and abrasion resistant effect and corrosion resistant protective effect.
In some embodiments, the amount of the functional nanomaterial modified by covalent bond or non-covalent bond in the outer resin is 0.5 wt% to 5 wt%, the amount of the photosensitizer or photoinitiator is 6 wt% to 10 wt%, and the rest is the fast curing resin, wherein wt% represents mass%. 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, nano cellulose fibers, carbon nanotube fibers, titanium carbide nano fibers and fluorocarbon fibers. The fiber cloth comprises different textile forms and can be obtained by blending two or more than two fibers. The fiber can comprise organic fiber, inorganic fiber or the composite of organic fiber and inorganic fiber, and the blended fiber can be obtained by compounding two fibers or by compounding multiple fibers.
The functional nano material comprises one of two-dimensional lamellar material, nano particles and rod-shaped nano material. Illustratively, the functional nanomaterial may be one of titanium carbide, graphite-phase carbon nitride, fluorinated graphene particles, spherical boron nitride particles, niobium carbide, and flake ultra-high molecular weight polyethylene.
As shown in fig. 1, another embodiment of the present invention provides a method for preparing the above protective coating, comprising the steps of:
coating a resin material on the damaged area of the metal material substrate, and preparing a resin material layer on the surface of the damaged area of the metal material substrate;
after surface modification, the fiber cloth is adhered to a resin material layer, and a fiber cloth layer is formed on the surface of the resin material layer;
adding a photosensitizer or a photoinitiator into a photocuring resin, uniformly mixing, carrying out modification treatment on a functional nano material to obtain a covalent bond or non-covalent bond modified functional nano material, adding the covalent bond or non-covalent bond modified functional nano material into the photocuring resin to obtain a photocuring composite resin, coating the photocuring composite resin on a fiber cloth layer, and forming a fast curing resin layer on the surface of the fiber cloth layer;
and irradiating the resin layer by adopting sunlight or ultraviolet band light for a set time to prepare 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-405 nm. When the protective coating for repairing the metal surface damage is irradiated by sunlight, the set time is 1-2 h, preferably 2 h; when the protective coating for repairing the metal surface damage is irradiated by ultraviolet band light, the set time is less than or equal to 10 min.
In addition, the protective coating of the embodiment is prepared by adding the functional nano material into the fast curing resin, so that the mechanical property, the erosion and wear resistance and the corrosion resistance of the fast curing resin are enhanced, and the requirement of long-life safety service of metal material matrixes such as steel pipe piles and the like in a severe marine environment is met.
The modification of the functional nanomaterial can be covalent bond modification or non-covalent bond modification, for example, the covalent bond modification is performed on the ultrahigh molecular weight polyethylene nanomaterial by using chitosan, or the graphene surface is modified by using supermolecular actions such as pi-pi interaction, ionic bonds and hydrogen bonds.
Wherein, the surface modification method of the fiber cloth comprises the following steps: the fiber cloth is firstly subjected to surface functionalization treatment, and then functionalized macromolecules are 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 the surface of the fiber cloth is provided with oxygen-containing functional groups, including carboxyl, amino or hydroxyl, and the like, and the surface of the functionalized fiber cloth is grafted with polydopamine, sulfonated chitosan, catecholamine, fluorine-containing thiol and the like, so that the interfacial compatibility and the interlayer 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 nano material is first surface modified, for example, the functional nano material is surface functionalized, including fluorination, surfactant treatment, grafting low surface energy substance, etc. And then carrying out multi-scale interface regulation and control treatment on the surface-modified functional nano material, and obtaining the composite material with different functionalities by regulating and controlling the content, combination form and distribution state of the nano material, so as to increase the dispersibility of the nano material in resin, improve the compatibility of the nano material and the resin and the interface shear strength, and further improve the mechanical property and the erosion and wear resistance of the composite material.
The invention also provides a composite material, which comprises a metal material substrate and a protective coating for repairing the damage of the metal surface, wherein the protective coating can be obtained by adopting the preparation method. Wherein the damage of the surface of the metal material substrate comprises corrosion damage and/or impact damage.
The present invention will be described in detail below with reference to specific examples.
Example 1
Adding a cationic photo-initiation material into epoxy acrylate, and uniformly mixing, wherein the content of the photo-initiation material is 5 wt%;
performing covalent bond modification on the ultrahigh molecular weight polyethylene nano material by adopting chitosan, and adding the ultrahigh molecular weight polyethylene nano material subjected to covalent bond modification with the mass fraction of 1 wt% into epoxy acrylate to obtain an epoxy acrylic composite resin coating;
coating epoxy resin on the surface of the steel pipe pile damaged by corrosion, and sticking the plain weave ultra-high molecular weight polyphenylene sulfide fiber cloth subjected to surface modification 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 fast-curing fiber cloth reinforced coating is completely cured after being irradiated for two hours under the sunlight to form a hard fiber cloth coating, namely the protective coating mentioned above.
As shown in fig. 2, which is an optical photograph of the surface of the fast curing fiber cloth reinforced coating prepared in this example, it can be seen from fig. 2 that the fast curing fiber cloth reinforced coating is well bonded, and no bubbling or separation occurs, which indicates that the interface of the bottom resin (i.e., the inner resin layer), the fiber cloth, and the surface nano-material reinforced fast curing resin (i.e., the outer fast curing resin layer) is well bonded. Therefore, the method of the embodiment can quickly repair the damage of the surface of the metal material, form the anticorrosive coating with high surface quality, and has good effects of erosion wear resistance and corrosion protection and good appearance. In addition, the surface of the nano material reinforced fast curing resin is smooth and has no pore cracks, and the like, which lays a good foundation for the erosion wear 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 eroded surface of the protective coating prepared in this example after 1 hour of erosion of the surface at a speed of 7m/s in a silicon carbide aqueous solution (silicon carbide weight fraction of 20 wt%), and it can be seen from FIG. 3 that the nano material reinforced fast curing resin has small erosion spot on the surface, small volume loss and mass loss after erosion, and can resist the impact of high-strength sand water flow, which shows that the nano material reinforced fast curing resin has excellent resistance to erosion and abrasion for a long time and exhibits long-life safety service performance. Therefore, it can be shown that 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, mainly because of the good dispersibility of the ultra-high molecular weight polyethylene nano-material in the fast curing resin, the interface performance between the ultra-high molecular weight polyethylene nano-material and the fast curing resin after the resin is cured is greatly improved, wherein the interface performance comprises interface compatibility and interface shear strength.
Fig. 4 is a graph of electrical impedance of the protective coating (the fiber cloth coating shown in the figure) prepared in this example, as shown in fig. 4, in which the abscissa represents Frequency (Frequency) in Hertz (HZ), the ordinate represents impedance in ohms (Ohm), and the Frequency and impedance magnitudes are expressed in logarithmic form. As can be seen from FIG. 4, the fiber cloth coating in this embodiment has a high impedance modulus, and the low frequency impedance value can reach 4 × 1011Ω/cm2And has excellent erosion resistance. For an anti-corrosion coating, the nano material reinforced rapid curing resin has an excellent effect of resisting the penetration of a corrosion medium, and the corrosion protection performance of the rapid curing resin in the subsequent process is improved.
Example 2
Adding a photosensitizer into the polyurethane acrylate, and uniformly mixing, wherein the content of the photosensitizer is 8 wt%, and adding 1 wt% of boron nitride nano material modified by a nanocellulose covalent bond into the polyurethane acrylate to obtain a polyurethane acrylate composite resin coating;
sticking twill aramid fiber cloth to the surface of the steel pipe pile coated with the epoxy resin and subjected to corrosion damage;
coating polyurethane acrylate composite resin paint on the surface of twilled 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 365nm wave band ultraviolet light for 2 minutes.
The fiber cloth coating in the embodiment has higher impedance modulus, and the low-frequency impedance value can reach 8 multiplied by 1011Ω/cm2And has excellent erosion resistance.
Example 3
Adding a photosensitizer into polyester acrylate, uniformly mixing, wherein the content of the photosensitizer is 6 wt%, and adding titanium carbide nano material modified by fluorosilane covalent bonds with the mass fraction of 1 wt% into the polyurethane acrylate to obtain a polyester acrylate composite resin coating;
sticking fiber cloth blended by glass fiber and carbon fiber to the surface of the steel pipe pile coated by epoxy resin and corroded to be damaged;
coating polyester acrylate composite resin paint on the surface of fiber cloth blended by glass fiber and carbon fiber 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 8 minutes of ultraviolet irradiation at 395nm wave band.
In the embodiment, the low-frequency impedance value of the fiber cloth coating can reach 5 multiplied by 1011Ω/cm2And has excellent erosion resistance.
Example 4
Adding a photo-initiation material into epoxy acrylate, uniformly mixing, wherein the content of the photo-initiation material is 6 wt%, and adding a fluorinated graphene nano material modified by a chitosan covalent bond with the mass fraction of 1 wt% into the epoxy acrylate to obtain an epoxy acrylate resin composite coating;
sticking fiber cloth blended by carbon fiber and aramid fiber to the surface of the steel pipe pile, which is corroded and damaged, and coating the epoxy resin on the surface of the steel pipe pile;
coating the epoxy acrylate resin composite coating on the surface of a fiber cloth blended by carbon fibers and aramid fibers to form a plain weave 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 for 3 minutes by ultraviolet light with a wave band of 330 nm.
In the embodiment, the low-frequency impedance value of the fiber cloth coating can reach 7.5 multiplied by 1011Ω/cm2And has excellent erosion resistance.
Example 5
Adding a photo-initiation material into epoxy acrylate, uniformly mixing, wherein the content of the photo-initiation material is 10 wt%, and adding a fluorinated graphene nano material modified by a chitosan covalent bond with a mass fraction of 5 wt% into the epoxy acrylate to obtain an epoxy acrylate resin composite coating;
sticking fiber cloth blended by carbon fiber and aramid fiber to the surface of the steel pipe pile, which is corroded and damaged, and coating the epoxy resin on the surface of the steel pipe pile;
coating the epoxy acrylate resin composite coating on the surface of a fiber cloth blended by carbon fibers and aramid fibers to form a plain weave 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 a wave band of 330nm for 5 minutes.
In the embodiment, the low-frequency impedance value of the fiber cloth coating can reach 8.0 multiplied by 1011Ω/cm2And has excellent erosion resistance.
Example 6
Adding a photo-initiation material into epoxy acrylate, uniformly mixing, wherein the content of the photo-initiation material is 6 wt%, and adding 0.5 wt% of fluorinated graphene nano material modified by a chitosan covalent bond into the epoxy acrylate to obtain an epoxy acrylate resin composite coating;
sticking fiber cloth blended by carbon fiber and aramid fiber to the surface of the steel pipe pile, which is corroded and damaged, and coating the epoxy resin on the surface of the steel pipe pile;
coating the epoxy acrylate resin composite coating on the surface of a fiber cloth blended by carbon fibers and aramid fibers to form a plain weave 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 a wave band of 330nm for 10 minutes.
In the embodiment, the low-frequency impedance value of the fiber cloth coating can reach 6.0 multiplied by 1011Ω/cm2And has excellent erosion resistance.
Although the present disclosure has been described above, the scope of the present disclosure is not limited thereto. Various changes and modifications may be effected therein by one of ordinary skill in the pertinent art without departing from the spirit and scope of the present disclosure, and these changes and modifications are intended to be within the scope of the present disclosure.

Claims (10)

1. The utility model provides a protective coating for repairing metal surface damage which characterized in that sets up in the regional surface of metal material base member damage, includes from interior to exterior set gradually in resin material layer, fibre cloth layer and the fast curing resin layer of the regional surface of metal material base member damage, wherein, the fibre cloth layer includes the fibre cloth through surface modification, the fast curing resin layer includes photosensitizer or photoinitiator, the fast curing resin layer still includes photocuring resin and the modified functional nano-material of covalent bond or non-covalent bond.
2. The protective coating for repairing damages on metal surfaces as claimed in claim 1, wherein the amount of the covalently or non-covalently modified functional nanomaterial is 0.5 wt% to 5 wt%, and the amount of the photosensitizer or the photoinitiator is 6 wt% to 10 wt%.
3. The protective coating for repairing damaged metal surfaces 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. The protective coating for repairing damage to a metal surface of claim 1 wherein said functional nanomaterials comprise one of two-dimensional sheet materials, nanoparticles, and rod-like nanomaterials.
5. The protective coating for repairing damage to a metal surface of claim 4, wherein said functional nanomaterial comprises one of titanium carbide, graphite phase carbon nitride, fluorinated graphene particles, spherical boron nitride particles, niobium carbide, and flaked ultra high molecular weight polyethylene.
6. A method for preparing a protective coating for repairing damage to a metal surface according to any one of claims 1 to 5, comprising:
coating a resin material on the damaged area of the metal material substrate, and preparing a resin material layer on the surface of the damaged area of the metal material substrate;
carrying out surface modification on fiber cloth, then adhering the fiber cloth to the resin material layer, and forming a fiber cloth layer on the surface of the resin material layer;
adding a photosensitizer or a photoinitiator into a photocuring resin, uniformly mixing, carrying out modification treatment on a functional nano material to obtain a covalent bond or non-covalent bond modified functional nano material, adding the covalent bond or non-covalent bond modified functional nano material into the photocuring resin to obtain a photocuring composite resin, coating the photocuring composite resin on the fiber cloth layer, and forming a quick curing resin layer on the surface of the fiber cloth layer;
and irradiating the rapid curing resin layer for a set time by adopting sunlight or ultraviolet band light to prepare the protective coating for repairing the damage of the metal surface.
7. The preparation method of the protective coating according to claim 6, wherein the surface modification method of the fiber cloth comprises the following steps: the fiber cloth is firstly subjected to surface functionalization treatment, and then functionalized macromolecules are grafted on the surface of the fiber cloth after the functionalization treatment.
8. The method for preparing the protective coating according to claim 6, wherein the modification treatment process of the functional nano material comprises the following steps: firstly, performing multi-surface modification on the functional nano material, and then performing multi-scale interface regulation and control treatment.
9. The preparation method of the protective coating according to claim 6, wherein when the protective coating for repairing damage of the metal surface is irradiated with sunlight, the set time is 1h to 2 h;
when the protective coating for repairing the metal surface damage is irradiated by ultraviolet band light, the wavelength range of the ultraviolet band light is 330nm-405nm, and the set time is less than or equal to 10 min.
10. A composite material comprising a metallic material substrate and a protective coating for repairing damage to a metallic surface according to any one of claims 1 to 5 or a protective coating for repairing damage to a metallic surface produced by a method of producing a protective coating according to any one of claims 6 to 9.
CN202111214285.5A 2021-10-19 2021-10-19 Protective coating for repairing metal surface damage, preparation method and composite material Active CN113914277B (en)

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