CN116063907A - Preparation of high-performance zinc-containing anticorrosive coating by shell-like pearl layer strategy - Google Patents

Preparation of high-performance zinc-containing anticorrosive coating by shell-like pearl layer strategy Download PDF

Info

Publication number
CN116063907A
CN116063907A CN202310259606.6A CN202310259606A CN116063907A CN 116063907 A CN116063907 A CN 116063907A CN 202310259606 A CN202310259606 A CN 202310259606A CN 116063907 A CN116063907 A CN 116063907A
Authority
CN
China
Prior art keywords
coating
nano
dimensional
zinc
shell
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202310259606.6A
Other languages
Chinese (zh)
Inventor
游波
雷洋
王海涛
马文霞
满衡
冯广宇
武利民
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shandong Shuntong Highway Engineering Co ltd
Zaozhuang Jiaoyun Investment Group Co ltd
Fudan University
Original Assignee
Shandong Shuntong Highway Engineering Co ltd
Zaozhuang Jiaoyun Investment Group Co ltd
Fudan University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shandong Shuntong Highway Engineering Co ltd, Zaozhuang Jiaoyun Investment Group Co ltd, Fudan University filed Critical Shandong Shuntong Highway Engineering Co ltd
Priority to CN202310259606.6A priority Critical patent/CN116063907A/en
Publication of CN116063907A publication Critical patent/CN116063907A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • 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
    • 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
    • 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
    • C09D179/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen, with or without oxygen, or carbon only, not provided for in groups C09D161/00 - C09D177/00
    • C09D179/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C09D179/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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
    • C09D5/10—Anti-corrosive paints containing metal dust
    • C09D5/106—Anti-corrosive paints containing metal dust containing Zn
    • 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
    • C09D5/24—Electrically-conducting 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/65—Additives macromolecular
    • 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
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0893—Zinc
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2265—Oxides; Hydroxides of metals of iron
    • C08K2003/2272—Ferric oxide (Fe2O3)

Abstract

The invention relates to a method for preparing a high-performance zinc-containing anti-corrosion coating by using a shell-like pearl layer strategy, which comprises the steps of mixing zinc powder, magnetic response conductive nano filler, matrix resin, unnecessary powder, unnecessary solvent and unnecessary auxiliary agent, obtaining the coating by adopting a physical mixing method, coating the coating by adopting a spraying, brushing or spin-coating method, and drying and curing the coating at 0-300 ℃ to obtain the high-performance zinc-containing anti-corrosion coating material. The corrosion-resistant coating material can take zinc powder as a sacrificial anode in an initial stage, protect a substrate from corrosion in a longer sacrificial anode stage, can effectively block penetration of a corrosive medium to a coating, has excellent shielding performance, and can protect a metal substrate for a long time. The preparation process is simple, the obtained anti-corrosion coating material can be used in the fields of surface protection, corrosion protection, decoration, electromagnetic shielding and the like of highway guardrails, buildings, new energy batteries, electric power, petrifaction, ships, bridges, power generation ocean facilities and the like, and has the advantages of light and thin coating, high compactness, high zinc powder utilization rate in the coating and capability of effectively reducing carbon emission.

Description

Preparation of high-performance zinc-containing anticorrosive coating by shell-like pearl layer strategy
Technical Field
The invention relates to a high-performance zinc-containing anti-corrosion coating prepared by a shell-like pearl layer strategy and a preparation method thereof, belonging to the technical field of functional materials.
Background
Zinc-rich coating has important position in the field of metal corrosion prevention, can still play a role in protecting the cathode of a durable sacrificial anode under the condition that the coating is mechanically damaged due to high corrosion prevention efficiency, and can be widely applied to the field of heavy corrosion prevention, such as steel structures with severe service conditions, such as expressway guardrails, ocean ships, bridges, offshore platforms and the like. For zinc-rich coatings, effective electrical contact between zinc powder and the protected metal substrate is a prerequisite to ensure that the sacrificial anode process occurs. However, during actual service of the zinc-rich coating, when insulating corrosion products accumulate on the surface of the zinc powder, the effective electrical contact between the zinc powder is broken, and the rest of the zinc powder cannot continue to act as sacrificial anode zinc, so that a great amount of zinc powder is wasted. In order to ensure sufficient reserves of anode zinc in the coating, the zinc powder content in the zinc-rich coating is generally up to 80%, which leads to poor compactness of the coating, the zinc-rich coating is difficult to serve as a barrier to continuously protect a metal substrate from corrosion medium after the sacrificial anode fails, and the coating is often rapidly failed after the sacrificial anode fails.
The shell nacreous layer has regular complex structure and is formed by stacking Wen Danceng and organic layers. Inspired by the layered stacked structure of the shell pearl layer, conductive flaky filler is introduced into the zinc-containing anti-corrosion coating to construct the lamellar structure of the shell-like pearl layer. The sheet filler has magnetic responsiveness after being modified, can be oriented parallel to the substrate under the drive of a magnetic field, can prolong the transmission path of corrosive media, prevent the corrosive media from diffusing to the interface of the metal substrate, and improve the shielding performance of the coating. Meanwhile, the conductive flaky filler can be connected with isolated zinc powder, so that the utilization rate of the zinc powder is improved, the consumption of the zinc powder is reduced, the compactness of the coating is further improved, and the light zinc-containing coating with high shielding performance and long-acting sacrificial anode protection is realized.
Disclosure of Invention
The invention aims to provide a high-performance zinc-containing anti-corrosion coating prepared by a shell-like pearl layer strategy and a preparation method thereof.
The zinc powder, the conductive nano filler, the matrix resin, the unnecessary powder, the unnecessary solvent and the unnecessary auxiliary agent are mixed, the transparent coating is obtained by adopting a physical mixing method, the coating is coated by adopting a spraying, brushing or spin coating method, and the coating is dried and cured at the temperature of 0-300 ℃ to obtain the high-performance zinc-containing anti-corrosion coating material prepared by the shell-like pearl layer strategy, so that the high-performance zinc-containing anti-corrosion coating material can effectively shield the penetration of corrosive medium to a metal substrate, and simultaneously has the efficient and durable sacrificial anode protection effect, and the substrate is protected from corrosion. The preparation process is simple, the obtained anti-corrosion coating material can be used in the fields of surface protection, corrosion protection, decoration, electromagnetic shielding and the like of highway guardrails, buildings, new energy batteries, electric power, petrifaction, ships, bridges, power generation ocean facilities and the like, and has the advantages of light and thin coating, high compactness, high zinc powder utilization rate in the coating and capability of effectively reducing carbon emission.
In order to achieve the above purpose, the invention adopts the following technical scheme: the invention provides a method for preparing a high-performance zinc-containing anti-corrosion coating by using a shell-like pearl layer strategy, which comprises the following steps: (a) at least one zinc powder having a size of 10 nm to 100 μm, (b) at least one magnetically responsive conductive nanofiller, (c) at least one matrix resin, (d) optionally powder, (e) optionally solvent, (f) optionally auxiliary agent; based on the total weight, the weight percentages of the components are as follows: 10-50% of zinc powder, 0.1-30% of magnetic response conductive nano filler, 0-20% of optional powder, 0-80% of optional solvent, 0-20% of optional auxiliary agent and the balance of matrix resin, wherein the total weight of the matrix resin is 100%, at least one of the necessary components (a) and (b) is a flaky filler, and the magnetic response conductive nano filler is a nano filler which builds magnetic response substances on the surface of a one-dimensional or two-dimensional nano material and has conductivity;
blending the raw materials (a) - (f) to prepare a coating liquid, coating the coating liquid by a brushing, spin coating or spraying method, and drying and curing the coating liquid in a magnetic field parallel to the direction of a metal substrate at 0-300 ℃ to obtain the shell-like pearl layer high-performance zinc-containing anti-corrosion coating material; the high-performance zinc-containing anticorrosive coating material is internally provided with a parallel arrangement structure of shell-like pearl layers, and the magnetic response conductive nano filler is induced by a magnetic field to be aligned in parallel with a metal substrate in a resin matrix, so that surrounding zinc powder is also aligned; the zinc powder, the magnetic response conductive nano filler and the matrix resin form a compact barrier in cross-parallel arrangement through bonding, so that penetration of corrosive media is hindered, and an electron transmission network formed by the zinc powder and the magnetic response conductive nano filler ensures electron transmission in chemical corrosion and ultra-long sacrificial anode protection duration time; the prepared coating has the thickness of less than 200 microns, high density, high zinc powder utilization rate in the coating and excellent corrosion resistance.
In the invention, the shell-like pearl layer structure is defined as a layered structure formed by orienting and stacking flaky fillers in a coating along a direction parallel to a substrate.
In the present invention, the magnetically responsive conductive nanofiller material comprises: (a) at least one-or two-dimensional nanomaterial, (b) at least one magnetically responsive substance precursor, (c) at least one dispersion medium, (d) at least one pH adjustor, and (e) optionally an auxiliary agent; based on the total weight, the weight percentages of the components are as follows: 0.1-10wt% of one-dimensional or two-dimensional nano material, 0.1-10wt% of magnetic response precursor, 0.1-5wt% of pH regulator, 0-10wt% of optional auxiliary agent and the balance of dispersion medium, wherein the total weight of the dispersion medium meets 100%; the (a) - (e) are subjected to any one of in-situ chemical reaction and chemical modification or heat treatment by raw materials to obtain the magnetic response conductive nano filler, wherein the magnetic response conductive nano filler material can be oriented under a magnetic field and has better electron transmission capability; the preparation method of the magnetic response conductive nano filler material comprises the following steps: dispersing one-dimensional or two-dimensional nano materials in a dispersing medium to obtain stable nano material dispersion liquid, regulating the pH value to 1-14 by using a pH regulator, adding a magnetic response substance precursor and optional additives into the dispersion liquid, stirring and reacting for 0.1-12h at the temperature of 5-100 ℃, precipitating and separating, washing and drying, and carrying out optional heat treatment to obtain the magnetic response conductive nano filler.
In the present invention, the zinc powder is defined as one or both of a spherical zinc powder or a flaky zinc powder.
In the invention, the matrix resin is one or more of epoxy resin, polyurethane resin, organic silicon resin, phenolic resin, amino resin, polyester resin, polyaspartic acid ester or acrylic resin.
Further, the matrix resin is not limited to any one or more of epoxy resin, aqueous polyurethane resin, aqueous acrylic resin, alkyd resin, UV-curable acrylic resin, UV-curable epoxy resin, UV-curable acrylate-polyurethane resin, aqueous silicone resin, and polyorganosiloxane resin.
In the invention, the unnecessary powder is one or more of coloring pigment, inorganic metal oxide, inorganic non-metal oxide, insoluble carbonate, insoluble sulfate, insoluble phosphate, insoluble chloride or natural mineral.
Further, the optional powder is not limited to any one of titanium dioxide, carbon black, iron oxide yellow, iron oxide red, cobalt blue, lithopone yellow, mica pearlescent pigment, silica, zirconia, alumina, zinc oxide, aluminum silicate, calcium carbonate, barium sulfate, barium phosphate, silver chloride, bentonite, perlite, or the like.
In the invention, the unnecessary solvent is one or more of water, alcohol solvents, benzene solvents, ether solvents, alcohol ether solvents, ketone solvents, ester solvents or hydrocarbon solvents.
Still further, the optional solvent is not limited to any one of deionized water, methanol, ethanol, isopropanol, n-butanol, propylene glycol, tetrahydrofuran, propylene glycol methyl ether, propylene glycol butyl ether, propylene glycol methyl ether acetate, propylene glycol butyl ether acetate, benzene, toluene, xylene, ethylene glycol methyl ether, acetone, pentanone, ethyl acetate, butyl acetate, and the like.
In the invention, the unnecessary auxiliary agent is one or more of a surfactant, a dispersing agent, a wetting agent, a thickening agent, a leveling agent, a defoaming agent, an anti-sagging agent, an anti-flash rust agent, a preservative, an anti-aging agent or a heat stabilizer which are commonly used in the coating.
Further, the optional auxiliary agent is exemplified by, but not limited to, any of sodium dodecyl sulfate, sodium polycarboxylate, ethylene oxide adduct, hydroxyethyl cellulose, polyether siloxane leveling agent, higher fatty acid glyceride, polyvinyl butyral, sodium benzoate, sodium nitrite, nano titanium dioxide, tribasic lead sulfate, and the like.
In the invention, the one-dimensional or two-dimensional nanomaterial in the magnetic response conductive nanofiller material is defined as a rod-shaped, fiber and lamellar material with one or two dimensions smaller than 100nm, and the one-dimensional or two-dimensional nanomaterial can be one or more of a nano carbon material, a nano metal oxide, a nano nonmetal oxide, a nano silicate, a nano sulfide, a nano nonmetal oxide, a two-dimensional transition metal carbon nitride (MXene) material or a natural nano two-dimensional lamellar material.
Further, the one-or two-dimensional nanomaterial is exemplified by, but not limited to, single-walled carbon nanotubes, multi-walled carbon nanotubes, and acidified carbonNanotube, nano zinc oxide, nano aluminum oxide, graphene oxide, reduced graphene oxide, nano talcum powder and Ti 3 C 2 T x MXene、Ti 2 CT x MXene、Ti 3 CNT x MXene、Mo 2 TiC 2 One or more of MXene, nano bentonite or nano kaolin, etc.
In the invention, the magnetically responsive substance precursor in the magnetically responsive conductive nanofiller material is defined as a magnetic metal ion salt.
Still further, the magnetically responsive material precursor is one or more of ferric chloride and its hydrate, ferrous chloride and its hydrate, ferric sulfate and its hydrate, ferrous sulfate and its hydrate, ferric nitrate and its hydrate, cobalt chloride and its hydrate, as non-limiting examples.
In the invention, the dispersion medium in the magnetic response conductive nano filler material is one or more of water, alcohol solvents, benzene solvents, ether solvents, alcohol ether solvents, ketone solvents, ester solvents or hydrocarbon solvents.
Still further, the dispersion medium is not limited to one or more of deionized water, methanol, ethanol, isopropyl alcohol, propylene glycol, tetrahydrofuran, propylene glycol methyl ether, propylene glycol butyl ether, propylene glycol methyl ether acetate, propylene glycol butyl ether acetate, benzene, toluene, xylene, ethylene glycol methyl ether, acetone, pentanone, ethyl acetate, butyl acetate, and the like.
In the invention, the pH regulator in the magnetic response conductive nano filler material is one or more of inorganic alkali, inorganic acid or organic acid.
Further, the pH adjustor in the step is one or more of ammonia water, sodium hydroxide, potassium hydroxide, perchloric acid, hydrochloric acid, sulfuric acid, glacial acetic acid, phosphoric acid, phytic acid, imidazole, or the like, as non-limiting examples.
In the invention, the optional auxiliary agent in the magnetic response conductive nano filler material is one or more of a conductive substance precursor, an oxidant, a surfactant, an acid catalyst, an alkaline catalyst or an initiator.
Still further, the optional auxiliary agent in the step is, but is not limited to, one or more of aniline, hydrogen peroxide, potassium dichromate, sodium dichromate, ammonium dichromate, potassium persulfate, sodium persulfate, ammonium persulfate, dodecylbenzenesulfonic acid, sodium dodecylbenzenesulfonate, sodium dodecyldiphenyloxide disulfonate, benzoyl peroxide, and azobisisobutyronitrile.
The invention provides a preparation method of a shell-like pearl layer high-performance zinc-containing anti-corrosion coating material, which comprises the following specific steps: blending the raw materials according to a proportion to prepare a coating liquid, coating the coating liquid by a brushing, spin coating or spraying method, and drying and solidifying the coating liquid in a magnetic field parallel to the direction of the metal substrate at 0-300 ℃ to obtain the shell-like pearl layer high-performance zinc-containing anti-corrosion coating material; under the induction of a magnetic field parallel to the metal substrate, the magnetically-responsive conductive nano filler and zinc powder are oriented and arranged in the coating along the magnetic field direction to form a layered structure of the shell-like pearl layer; the shell-like pearl layer layered structure can prolong the diffusion path of the corrosive medium, and can be used as a tight barrier to protect the metal substrate from being corroded by the corrosive medium in the initial stage of the coating and the protection stage after the sacrificial anode is in failure; meanwhile, the magnetic response conductive nano filler and zinc powder are in contact with each other and the metal substrate to form an electron transmission network, so that the utilization rate of the zinc powder is improved, and the duration of the sacrificial anode protection stage is greatly prolonged.
In the preparation method of the precursor of the magnetic response substance, firstly, the one-dimensional or two-dimensional nano material is modified with magnetic response nano particles, and the one-dimensional or two-dimensional nano material is endowed with magnetic response characteristics, so that alignment along the magnetic field direction can be performed in the coating under the induction of a magnetic field; then the magnetic response one-dimensional or two-dimensional nano material is provided with conductivity through an optional in-situ chemical reduction or chemical modification or heat treatment step; the method comprises the following steps: dispersing one-dimensional or two-dimensional nano materials in a dispersing medium to obtain stable nano material dispersion, regulating the pH value to 1-14 by using a pH regulator, adding a magnetic response substance precursor and optional additives into the nano material dispersion after regulating the pH value, stirring and reacting for 0.1-12h at the temperature of 5-100 ℃, precipitating and separating, washing and drying, and obtaining the magnetic response conductive nano filler after optional heat treatment.
According to the invention, the magnetic response conductive nano filler material can be oriented and arranged along the magnetic field direction under the induction of the magnetic field parallel to the metal substrate, and meanwhile, the zinc powder around the conductive nano filler material is driven to rotate, and finally, in the solidified coating, the zinc powder is also oriented along the magnetic field direction, so that the layered structure of the shell-like pearl layer can prolong the diffusion path of a corrosive medium, and can be used as a tight barrier to protect the metal substrate from being corroded by the corrosive medium in the initial stage of the coating and the protection stage after the sacrificial anode is in failure; meanwhile, the magnetic response conductive nano filler and zinc powder are in contact with each other and the metal substrate to form an electron transmission network, so that the utilization rate of the zinc powder is improved, and the duration of the sacrificial anode protection stage is greatly prolonged.
The shell-like nacreous layer strategy provided by the invention is used for preparing the high-performance zinc-containing anti-corrosion coating material as a composite coating material under the combined action of two mechanisms of shielding protection and sacrificial anode protection, and can be applied to the surfaces of various metal substrates.
The invention uses an in-situ chemical method to modify one-dimensional or two-dimensional nano materials, loads magnetically responsive nano particles on the nano materials, and prepares the magnetically responsive conductive nano materials through subsequent heat treatment or chemical modification steps. Firstly, modifying magnetic response nano particles on a one-dimensional or two-dimensional nano material, endowing the one-dimensional or two-dimensional nano material with magnetic response characteristics, and carrying out alignment oriented along the magnetic field direction in the coating under the induction of a magnetic field. The magnetically responsive one-or two-dimensional nanomaterial is then rendered conductive by in situ chemical reduction or chemical modification or heat treatment steps.
According to the high-performance zinc-containing anti-corrosion coating material prepared by the shell-like pearl layer strategy, zinc powder and magnetic-response conductive nano fillers can be aligned along the magnetic field direction under the drive of a magnetic field parallel to a substrate, so that a compact barrier formed by cross-linking and parallel arrangement of the zinc powder, the magnetic-response conductive nano fillers and a resin matrix and an electron transmission network formed by the zinc powder and the conductive nano fillers are formed in the coating, the compactness and zinc powder utilization rate of the coating can be improved simultaneously, the anti-corrosion protection duration of the coating is greatly prolonged, and the excellent anti-corrosion performance under the combined action of double mechanisms is achieved.
The invention has the beneficial effects that: the operation method is simple, and the modification effect is obvious. The magnetically responsive conductive nanofiller material can be obtained by in situ chemical modification and optional heat treatment steps. The magnetic response conductive nano filler material has sensitive magnetic response and higher conductivity, can be oriented under the drive of a magnetic field, and can construct an electron transmission path on zinc powder which is communicated and isolated. The zinc powder, the magnetic response conductive nano filler, the resin, optional powder, the solvent and the auxiliary agent are blended to obtain coating liquid, and the coating can be coated on a metal substrate by means of conventional brushing, spin coating, spraying and the like, and the coating with a shell-like pearl layer structure can be obtained only by applying a magnetic field in the curing process. The coating with optimal anticorrosion performance can be conveniently regulated and controlled by the application of a magnetic field, the type of matrix resin, the coating process and the filler addition. The prepared coating has high shielding protection effect and long-time sacrificial anode protection effect, and shows excellent corrosion resistance. The invention has simple preparation process, light and thin coating, high density and high zinc powder utilization rate in the coating, can be applied to the surfaces of various metal substrates, and can also be used in the fields of electromagnetic shielding, electric conduction and heat conduction anti-corrosion coatings.
All percentages and ratios used herein are by weight unless otherwise indicated.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) photograph of shell nacre coating.
Fig. 2 is a Scanning Electron Microscope (SEM) photograph of a magnetically responsive conductive reduced graphene oxide prepared in example 1.
Fig. 3 is a hysteresis loop obtained by testing the magnetically responsive conductive reduced graphene oxide prepared in example 1 at room temperature.
Fig. 4 is an SEM image of a cross section of the coating material prepared in example 5.
Fig. 5 is an image of electrochemical impedance spectra of (a) open circuit potential and (b) first day of a soak test of the coating material prepared in example 5.
FIG. 6 shows the corrosion of the substrate after 250h salt spray test of example 5, (a) a pure epoxy coating and (b) the coating described in example 5.
Detailed Description
For further illustrating the present invention, the present invention is exemplified by the following examples, but the present invention is not limited to the following examples.
Example 1
A magnetic response conductive nano filler and a preparation method thereof specifically comprises the following steps:
dispersing 100mg of graphene oxide in 50mL of deionized water, performing ultrasonic treatment for 2 hours to obtain stable graphene oxide dispersion liquid, adding ammonia water into the stable graphene oxide dispersion liquid to adjust the pH value to be alkaline, stirring for 30 minutes to obtain a stable system, and adding 1g of FeCl into the stable system 2 The reaction was continued for 3 hours, the product was collected by a magnetic separation method, and washed three times with ethanol and dried overnight in a vacuum oven at 40 ℃ to obtain a magnetically responsive conductive reduced graphene oxide. Wherein Fe is 2+ In-situ oxidation-reduction reaction with graphene oxide to obtain Fe 3+ And reducing graphene oxide while Fe 3+ And precipitating under alkaline environment to generate magnetic hematite.
As shown in FIG. 2, a Scanning Electron Microscope (SEM) photograph of the magnetically responsive conductive reduced graphene oxide prepared in example 1, wherein the reduced graphene oxide is loaded with high density magnetic hematite nanoparticles.
As shown in fig. 3, a hysteresis loop obtained by testing the magnetically responsive conductive reduced graphene oxide prepared in example 1 at room temperature.
Example 2
A magnetic response conductive nano filler and a preparation method thereof specifically comprises the following steps:
dispersing 0.5g of bentonite in 50g of ethanol and stripping to obtain a stable bentonite dispersion, adding 0.3g of ferric chloride hexahydrate and 0.1g of ferrous chloride tetrahydrate into the graphene oxide dispersion under nitrogen atmosphere, stirring for 1h, regulating the pH value of the system to 9-14 by using ammonia water, continuing to react for 1h under vigorous stirring, standing for precipitation, magnetically separating, washing by ethanol and drying to obtain magnetically-responsive bentonite, dissolving 100mg of polyaniline in 100mL of tetrahydrofuran, performing ultrasonic treatment for 30min, adding the magnetically-responsive bentonite into the tetrahydrofuran solution of polyaniline, and performing ultrasonic treatment for 3-6h to obtain the uniform magnetically-responsive conductive flaky polyaniline-bentonite material.
Example 3
A magnetic response conductive nano filler and a preparation method thereof specifically comprises the following steps:
dispersing 100mg of acidified carbon nano tubes in 100mL of ethanol to obtain stable acidified carbon nano tube dispersion liquid, adding 30% NaOH solution into the dispersion liquid to adjust the pH value of the system to be alkaline, adding 0.4g of ferric sulfate and 0.8g of ferrous sulfate into the dispersion liquid, stirring for 1h, standing for precipitation, magnetically-decanting for separation, washing with ethanol, drying to obtain magnetically-responsive carbon nano tubes, and carrying out heat treatment on the magnetically-responsive carbon nano tubes in nitrogen atmosphere at 500 ℃ for 6h to obtain the magnetically-responsive conductive carbon nano tubes.
Example 4
A magnetic response conductive nano filler and a preparation method thereof specifically comprises the following steps:
because the two-dimensional transition metal carbon nitrogen compound (MXene) material has excellent conductive performance, only the MXene needs to be subjected to magnetic response modification to obtain the magnetic response conductive MXene. Dispersing 100mg of two-dimensional nano MXene material in 50g of deionized water to obtain stable MXene material dispersion, adding 1g of ferric sulfate and 0.2g of ferrous sulfate into the MXene dispersion, stirring for 1h, regulating the pH value of the system to be alkaline by using 30% NaOH solution, continuing to react for 6h, standing for precipitation, separating by magnetic separation, washing by deionized water, and drying to obtain the magnetic response conductive MXene.
Example 5
An ultra-high performance zinc-containing anti-corrosion coating material with a shell-like pearl layer structure and a preparation method thereof comprise the following specific steps:
the magnetic response conductive reduced graphene oxide 1wt%, flaky zinc powder 30wt%, water-based epoxy resin 28wt%, curing agent 7wt% and propylene glycol methyl ether 34wt% of the magnetic response conductive reduced graphene oxide of the embodiment 1 are mixed, the coating is sprayed on the surface of carbon steel by a spray gun in a magnetic field parallel to carbon steel, and the coating is cured at room temperature, so that the ultra-high performance zinc-containing anti-corrosion epoxy coating with a shell-like pearl layer structure can be obtained.
As shown in fig. 4, SEM images of cross sections of the coating prepared in example 5 showed that both the flake zinc powder and the magnetically responsive conductive reduced graphene oxide were capable of being aligned in parallel therein to form a layered structure similar to a shell nacre coating.
As shown in fig. 5, the coated sacrificial anode prepared in example 5 has a cathodic protection duration of more than 99 days, and has a very high initial resistance value, and the shielding performance of the coating material is very excellent.
Example 6
An ultra-high performance zinc-containing anti-corrosion coating material with a shell-like pearl layer structure and a preparation method thereof comprise the following specific steps:
the magnetically responsive conductive sheet polyaniline-bentonite of example 2 was mixed with 5wt%, spherical zinc powder 25wt%, cobalt blue 10wt%, aqueous epoxy resin 30wt%, aqueous amine curing agent 5wt%, deionized water 23wt% and defoamer 2wt% and then coated on the surface of a metal substrate with a 200 μm wire rod, and the coating was cured at 80 ℃ in a magnetic field to obtain an ultra-high performance zinc-containing corrosion-resistant coating material having a shell-like nacreous layer structure.
Example 7
An ultra-high performance zinc-containing anti-corrosion coating material with a shell-like pearl layer structure and a preparation method thereof comprise the following specific steps:
the magnetic response conductive carbon nano tube 5wt%, sheet zinc powder 30wt%, polyaspartic acid ester resin 55wt%, dimethylbenzene 5wt% and wetting dispersant 5wt% of the embodiment 3 are uniformly mixed, and then the mixture is coated on the surface of a metal substrate by a 100 mu m wire rod, and the coating is cured in a magnetic field at 50 ℃ to obtain the light and thin ultra-high-performance zinc-containing anti-corrosion coating material with a shell-like pearl layer structure.
Example 8
An ultra-high performance zinc-containing anti-corrosion coating material with a shell-like pearl layer structure and a preparation method thereof comprise the following specific steps:
the magnetic response conductive two-dimensional transition metal carbon-nitrogen compound (MXene) material of the embodiment 4, the spherical zinc powder, the aqueous hydroxy acrylic resin 50wt%, the aqueous polyurethane resin 20wt% and the defoamer 5wt% are uniformly mixed, the coating is coated on the surface of a metal substrate by a spin coating method, and the coating is dried at room temperature under a magnetic field and crosslinked and solidified to obtain the light and thin ultra-high performance zinc-containing anti-corrosion coating material with the shell-like pearl layer structure. Table 1 shows the initial resistance and the duration of salt spray resistance of the high performance zinc-containing corrosion-resistant coatings described in examples 5-8 having a shell-like nacre coating structure.
Figure BDA0004130716950000091
Figure BDA0004130716950000101
/>

Claims (10)

1. A method for preparing a high-performance zinc-containing anticorrosive coating by using a shell-like pearl layer strategy is characterized by comprising the following steps of: the coating material comprises: (a) at least one zinc powder having a size of 10 nm to 100 μm, (b) at least one magnetically responsive conductive nanofiller, (c) at least one matrix resin, (d) optionally powder, (e) optionally solvent, (f) optionally auxiliary agent; based on the total weight, the weight percentages of the components are as follows: 10-50% of zinc powder, 0.1-30% of magnetic response conductive nano filler, 0-20% of optional powder, 0-80% of optional solvent, 0-20% of optional auxiliary agent and the balance of matrix resin, wherein the total weight of the matrix resin is 100%, at least one of the necessary components (a) and (b) is a flaky filler, and the magnetic response conductive nano filler is a nano filler which builds magnetic response substances on the surface of a one-dimensional or two-dimensional nano material and has conductivity;
blending the raw materials (a) - (f) to prepare a coating liquid, coating the coating liquid by a brushing, spin coating or spraying method, and drying and curing the coating liquid in a magnetic field parallel to the direction of a metal substrate at 0-300 ℃ to obtain the shell-like pearl layer high-performance zinc-containing anti-corrosion coating material; the high-performance zinc-containing anticorrosive coating material is internally provided with a parallel arrangement structure of shell-like pearl layers, and the magnetic response conductive nano filler is induced by a magnetic field to be aligned in parallel with a metal substrate in a resin matrix, so that surrounding zinc powder is also aligned; the zinc powder and the magnetic response conductive nano filler and matrix resin form a cross-linked and parallel arranged compact barrier coating through the bonding actions of hydrogen bonds, chemical bonds and the like, so that penetration of corrosive media is hindered, and an electron transmission network formed by the zinc powder and the magnetic response conductive nano filler ensures electron transmission in chemical corrosion and ensures the sacrificial anode protection duration time; the prepared coating has the thickness of less than 200 microns, high density, high zinc powder utilization rate in the coating and excellent corrosion resistance.
2. The method for preparing the high-performance zinc-containing anticorrosive coating by using the shell-like pearl layer strategy according to claim 1, which is characterized in that: the magnetically-responsive conductive nanofiller includes: (a) at least one-or two-dimensional nanomaterial, (b) at least one magnetically responsive substance precursor, (c) at least one dispersion medium, (d) at least one pH adjustor, and (e) optionally an auxiliary agent; based on the total weight, the weight percentages of the components are as follows: 0.1-10wt% of one-dimensional or two-dimensional nano material, 0.1-10wt% of magnetic response precursor, 0.1-5wt% of pH regulator, 0-10wt% of optional auxiliary agent and the balance of dispersion medium, wherein the total weight of the dispersion medium meets 100%; the raw materials (a) - (e) are subjected to any one of in-situ chemical reaction, chemical modification or heat treatment to obtain the magnetic response conductive nano-filler, wherein the magnetic response conductive nano-filler can be oriented under a magnetic field and has good electron transmission capability; the preparation method of the magnetic response conductive nano filler comprises the following steps: dispersing one-dimensional or two-dimensional nano materials in a dispersing medium to obtain stable nano material dispersion, regulating the pH value to 1-14 by using a pH regulator, adding a magnetic response substance precursor and optional additives into the nano material dispersion after regulating the pH value, stirring and reacting for 0.1-12h at the temperature of 5-100 ℃, precipitating and separating, washing and drying, and obtaining the magnetic response conductive nano filler after optional heat treatment.
3. The method for preparing the high-performance zinc-containing anticorrosive coating by using the shell-like pearl layer strategy according to claim 1, which is characterized in that: the zinc powder is one or two of spherical zinc powder and flaky zinc powder.
4. The method for preparing the high-performance zinc-containing anticorrosive coating by using the shell-like pearl layer strategy according to claim 1, which is characterized in that: the matrix resin is one or more of epoxy resin, polyurethane resin, organic silicon resin, phenolic resin, amino resin, polyester resin, polyaspartic acid ester or acrylic resin.
5. The method for preparing the high-performance zinc-containing anticorrosive coating by using the shell-like pearl layer strategy according to claim 1, which is characterized in that: the non-essential powder is one or more of coloring pigment, inorganic metal oxide, inorganic non-metal oxide, insoluble carbonate, insoluble sulfate, insoluble phosphate, insoluble chloride or natural mineral.
6. The method for preparing the high-performance zinc-containing anticorrosive coating by using the shell-like pearl layer strategy according to claim 1, which is characterized in that: the non-essential solvent is one or more of water, alcohol solvents, benzene solvents, ether solvents, alcohol ether solvents, ketone solvents, ester solvents or hydrocarbon solvents.
7. The method for preparing the high-performance zinc-containing anticorrosive coating by using the shell-like pearl layer strategy according to claim 1, which is characterized in that: the optional auxiliary agent is one or more of a common surfactant, a dispersing agent, a wetting agent, a thickening agent, a leveling agent, a defoaming agent, an anti-sagging agent, an anti-flash rust agent, a preservative, an anti-aging agent and a heat stabilizer in the coating.
8. The method for preparing the high-performance zinc-containing anticorrosive coating by using the shell-like pearl layer strategy according to claim 2, which is characterized in that: the one-dimensional or two-dimensional nano material in the magnetic response conductive nano filler is a rod-shaped, fiber or lamellar material with one or two dimensions smaller than 100nm, and is specifically one or more of a nano carbon material, a nano metal oxide, a nano non-metal oxide, a nano silicate, a nano sulfide, a nano non-metal oxide, a two-dimensional transition metal carbon nitride (MXene) material or a natural nano two-dimensional lamellar material; the magnetic response substance precursor is magnetic metal ion salt; the dispersion medium is one or more of water, alcohol solvents, benzene solvents, ether solvents, alcohol ether solvents, ketone solvents, ester solvents or hydrocarbon solvents; the pH regulator is one or more of inorganic alkali, inorganic acid or organic acid; the optional auxiliary agent is one or more of a conductive substance precursor, an oxidant, a surfactant, an acid catalyst, a basic catalyst or an initiator.
9. A method for preparing the shell-like pearl layer-imitated zinc-containing anti-corrosive coating material with high performance according to claim 2, which is characterized by comprising the following specific steps: blending the raw materials according to a proportion to prepare a coating liquid, coating the coating liquid by a brushing, spin coating or spraying method, and drying and solidifying the coating liquid in a magnetic field parallel to the direction of the metal substrate at 0-300 ℃ to obtain the shell-like pearl layer high-performance zinc-containing anti-corrosion coating material; under the induction of a magnetic field parallel to the metal substrate, the magnetically-responsive conductive nano filler and zinc powder are oriented and arranged in the coating along the magnetic field direction to form a layered structure of the shell-like pearl layer; the shell-like pearl layer layered structure can prolong the diffusion path of the corrosive medium, and can be used as a tight barrier to protect the metal substrate from being corroded by the corrosive medium in the initial stage of the coating and the protection stage after the sacrificial anode is in failure; meanwhile, the magnetic response conductive nano filler and zinc powder are in contact with each other and the metal substrate to form an electron transmission network, so that the utilization rate of the zinc powder is improved, and the duration of the sacrificial anode protection stage is greatly prolonged.
10. The method of manufacturing according to claim 9, wherein: firstly, modifying magnetic response nano particles on a one-dimensional or two-dimensional nano material, endowing the one-dimensional or two-dimensional nano material with magnetic response characteristics, and arranging the one-dimensional or two-dimensional nano material in the coating along the orientation of the magnetic field under the induction of the magnetic field; then the magnetic response one-dimensional or two-dimensional nano material is provided with conductivity through an optional in-situ chemical reduction or chemical modification or heat treatment step; the method comprises the following steps: dispersing one-dimensional or two-dimensional nano materials in a dispersing medium to obtain stable nano material dispersion, regulating the pH value to 1-14 by using a pH regulator, adding a magnetic response substance precursor and optional additives into the nano material dispersion after regulating the pH value, stirring and reacting for 0.1-12h at the temperature of 5-100 ℃, precipitating and separating, washing and drying, and obtaining the magnetic response conductive nano filler after optional heat treatment.
CN202310259606.6A 2023-03-17 2023-03-17 Preparation of high-performance zinc-containing anticorrosive coating by shell-like pearl layer strategy Pending CN116063907A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202310259606.6A CN116063907A (en) 2023-03-17 2023-03-17 Preparation of high-performance zinc-containing anticorrosive coating by shell-like pearl layer strategy

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202310259606.6A CN116063907A (en) 2023-03-17 2023-03-17 Preparation of high-performance zinc-containing anticorrosive coating by shell-like pearl layer strategy

Publications (1)

Publication Number Publication Date
CN116063907A true CN116063907A (en) 2023-05-05

Family

ID=86175226

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202310259606.6A Pending CN116063907A (en) 2023-03-17 2023-03-17 Preparation of high-performance zinc-containing anticorrosive coating by shell-like pearl layer strategy

Country Status (1)

Country Link
CN (1) CN116063907A (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111205738A (en) * 2020-03-06 2020-05-29 涂创时代(苏州)科技开发有限公司 Low-zinc anticorrosive composition compounded by graphene and flaky conductive material and application thereof
CN114773959A (en) * 2022-05-31 2022-07-22 复旦大学 High-performance transparent anticorrosive coating material and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111205738A (en) * 2020-03-06 2020-05-29 涂创时代(苏州)科技开发有限公司 Low-zinc anticorrosive composition compounded by graphene and flaky conductive material and application thereof
CN114773959A (en) * 2022-05-31 2022-07-22 复旦大学 High-performance transparent anticorrosive coating material and preparation method thereof

Similar Documents

Publication Publication Date Title
Hosseinpour et al. Recent advances and future perspectives for carbon nanostructures reinforced organic coating for anti-corrosion application
Sazou et al. Conducting polyaniline nanocomposite-based paints for corrosion protection of steel
CN107459906B (en) Corrosion-resistant composite layer
CN114773959B (en) High-performance transparent anticorrosive coating material and preparation method thereof
CN113604151B (en) Preparation method of phosphated polyaniline-silicon dioxide graft modified graphene/waterborne epoxy-containing silicon resin composite coating
CN113683956B (en) Preparation method of graphene-silicon dioxide bonded grafted polyaniline/aqueous epoxy-containing silicon resin composite coating
CN110746796B (en) Modified graphene and preparation method of slurry containing modified graphene
Wang et al. Co-modification of nano-silica and lysine on graphene oxide nanosheets to enhance the corrosion resistance of waterborne epoxy coatings in 3.5% NaCl solution
CN110305559B (en) Corrosion-resistant heat-conducting coating and preparation method thereof
CN112457698A (en) Graphene-modified zinc powder, preparation method and application of graphene-modified zinc powder in zinc-rich anticorrosive coating
WO2021068506A1 (en) Water-based anticorrosive coating based on graphene oxide and preparation method therefor
CN107760205B (en) Water-based carbon steel surface treating agent based on polypyrrole/graphene composite material
CN115627092A (en) Water-based paint and preparation method thereof
Fei et al. Anti-corrosion and electrically conductive inorganic conversion coatings based on aligned graphene derivatives by electrodeposition
Yao et al. Application of nanomaterials in waterborne coatings: A review
CN101717608B (en) Conductive anti-corrosion coating of electric power grounding grid and preparation method thereof
Xiao et al. Mussel-inspired preparation of superhydrophobic mica nanosheets for long-term anticorrosion and self-healing performance of epoxy coatings
Zhang et al. Performance enhancement of the anti-corrosion coating based on Ce 3+-polyaniline–montmorillonite composite/epoxy-ester system
CN111876005A (en) Anti-corrosion photovoltaic cable coating and preparation method thereof
Chen et al. A facile cathodic electrophoretic deposition (EPD) of GO nanosheet with an orderly layered nanostructure for development of long-term durability anticorrosive coating
CN111253778A (en) Preparation method of modified boron nitride nanosheet and application of modified boron nitride nanosheet
Li et al. Preparation of Fe3O4/PANI nanocomposite and its metal anticorrosive activity
Bian et al. One-step electrodeposition of polypyrrole/Ti3C2Tx MXene composite coating for 304SS bipolar plates in PEMFC
CN112029314A (en) Nano-filler and preparation method and application thereof
CN108752987A (en) A kind of preparation method and applications of graphene-oxide composite coating

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination