CN116179001A - Preparation method and application method of water-based chromium-free composite coating and coating thereof - Google Patents

Preparation method and application method of water-based chromium-free composite coating and coating thereof Download PDF

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CN116179001A
CN116179001A CN202211576614.5A CN202211576614A CN116179001A CN 116179001 A CN116179001 A CN 116179001A CN 202211576614 A CN202211576614 A CN 202211576614A CN 116179001 A CN116179001 A CN 116179001A
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coating
agent
water
free composite
based chromium
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Inventor
彭如意
付赛君
肖启亮
徐清
周宏福
王�章
贺才进
冯非易
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Hengyang Taihao Communication Vehicles Co Ltd
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Hengyang Taihao Communication Vehicles Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/10—Anti-corrosive paints containing metal dust
    • C09D5/106—Anti-corrosive paints containing metal dust containing Zn
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D1/00—Processes for applying liquids or other fluent materials
    • B05D1/36—Successively applying liquids or other fluent materials, e.g. without intermediate treatment
    • B05D1/38—Successively applying liquids or other fluent materials, e.g. without intermediate treatment with intermediate treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0209—Multistage baking
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254—After-treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/10—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by other chemical means
    • B05D3/102—Pretreatment of metallic substrates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/12—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by mechanical means
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50—Multilayers
    • B05D7/52—Two layers
    • B05D7/54—No clear coat specified
    • B05D7/544—No clear coat specified the first layer is let to dry at least partially before applying the second layer
    • 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
    • C09D5/103—Anti-corrosive paints containing metal dust containing Al
    • 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
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612—Non-macromolecular compounds
    • C09D5/1618—Non-macromolecular compounds inorganic
    • 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
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1687—Use of special additives

Abstract

A preparation method and a use method of a water-based chromium-free composite coating and a coating thereof relate to the technical field of anti-corrosion coatings, and comprise the following raw materials: zinc aluminum powder, an antifouling agent, an adhesive, a corrosion inhibitor, a dispersing agent, a protective agent, a thickening agent, a defoaming agent and deionized water. The coating prepared by the invention can be coated on a substrate to obtain a coating with good adhesive force and corrosion resistance, and meanwhile, the use of hexavalent chromium is avoided, so that the environmental pollution is less influenced.

Description

Preparation method and application method of water-based chromium-free composite coating and coating thereof
Technical Field
The invention relates to the technical field of anti-corrosion coatings, in particular to a water-based chromium-free composite coating and a preparation method and a use method of the coating.
Background
In the human marine activities such as ocean capital construction, ship operation, etc., serious problems of metal corrosion and biofouling are faced. These problems can lead to reduced sailing efficiency, impact on marine and base station mat acoustic instrumentation, cause pipe blockage, malfunction of various instrumentation and machinery, and accelerated collective corrosion.
The methods for preventing and treating marine biofouling to reduce metal corrosion are mainly physical antifouling methods, electrolytic methods, antifouling metals or alloys, and antifouling coatings. Practice proves that the method for applying the antifouling coating to prevent the pollution is the most economical and effective method, which is mainly to apply a layer of antifouling coating on the surface of a substrate, so that toxic substances are slowly released from the coating in seawater, and the growth of fouling organisms is inhibited. However, the existing antifouling paint coating has the problems of environmental pollution and the like.
Disclosure of Invention
The invention aims to provide an aqueous chromium-free composite coating which is used for forming a stain-resistant and corrosion-resistant composite coating on the surface of metal and simultaneously reducing the pollution to the environment.
In order to solve the technical problems, the invention adopts the following technical scheme: an aqueous chromium-free composite coating comprises the following raw materials: zinc aluminum powder, an antifouling agent, an adhesive, a corrosion inhibitor, a dispersing agent, a protective agent, a thickening agent, a defoaming agent and deionized water.
Preferably, the raw materials comprise the following components in percentage by weight: 3.5g of zinc aluminum powder, 1.5g of antifouling agent, 2g of adhesive, 0.35g of corrosion inhibitor, 0.40g of dispersing agent, 1.6g of protective agent, 0.1g of thickening agent, 3-4 drops of defoaming agent and the balance of deionized water; wherein the antifouling agent is copper powder; the adhesive is AC-66, namely gamma-glycidyl ether propyl trimethoxysilane, which can improve the adhesion of the polymer coating or adhesive to metal or other polymer surfaces; the corrosion inhibitor is Mo 12 Na 3 O 40 P is as follows; the dispersing agent is Tween 20 (CH) 2 OH） 2 The two components are mixed to form a dispersing agent, and the specific mixing proportion is not limited; the thickener is hydroxyethyl cellulose; the specific choice of the protectant and defoamer may be conventional and is therefore not limited.
The method for preparing the water-based chromium-free composite coating comprises the following steps:
adding a proper amount of adhesive, dispersing agent, protective agent, defoaming agent and deionized water into a container, then slowly adding zinc-aluminum powder and an anti-fouling agent under the stirring of a heat-collecting constant-temperature heating magnetic stirrer, adding a proper amount of corrosion inhibitor and thickener after the zinc-aluminum powder and the anti-fouling agent are wetted, and finally stirring for about 3 hours until all the components are uniformly mixed to obtain the outer-layer water-based chromium-free composite coating;
adding a proper amount of adhesive, dispersing agent, protective agent, defoaming agent and deionized water into a container, then slowly adding zinc aluminum powder under stirring of a heat-collecting constant-temperature heating magnetic stirrer, adding a proper amount of corrosion inhibitor and thickening agent after the zinc aluminum powder is wetted, and finally stirring for about 3 hours until all components are uniformly mixed to obtain the inner-layer water-based chromium-free composite coating.
The application method of the water-based chromium-free composite coating comprises the following steps:
pretreatment: grinding the surface of the matrix with sand paper to remove rust, then soaking in alkaline solution for 40 minutes to remove oil, then cleaning with alcohol and drying for later use;
primary coating: dip-coating a matrix into the inner-layer water-based chromium-free composite coating, removing redundant solution on the surface of the matrix to ensure that the surface of the prepared coating is uniform, drying and sintering, and cooling at room temperature to obtain the matrix coated with the inner-layer water-based chromium-free composite coating;
and (3) secondary coating: dip-coating the substrate obtained after primary coating into an outer layer water-based chromium-free composite coating, removing redundant solution on the surface of the substrate to ensure that the surface of the prepared coating is uniform, drying and sintering, and cooling at room temperature to obtain the substrate coated with the composite coating.
Preferably, the excess solution is thrown off the surface by rotating the substrate during both the primary and secondary coating steps.
More preferably, in the primary coating and the secondary coating steps, the drying and sintering modes are that the primary drying is performed for 8-10 minutes and the secondary drying is performed for 25-30 minutes.
More preferably, the pre-bake temperature is 100 ℃ and the sintering temperature is 280 ℃.
The coating prepared by the invention can be coated on a substrate to obtain a coating with good adhesive force and corrosion resistance, and meanwhile, the use of hexavalent chromium is avoided, so that the environmental pollution is less influenced.
Drawings
FIG. 1 is a SEM schematic of a cross-section of a coating according to an embodiment of the invention;
fig. 2 is a schematic SEM of the surface of the coating according to an embodiment of the invention.
Detailed Description
The invention will be further described with reference to examples and drawings, to which reference is made, but which are not intended to limit the scope of the invention.
Example 1
1g of adhesive (AC-66), dispersant (Tween 20 and (CH) 2 OH） 2 ) Adding 0.40g of protective agent 1.6g, 3-4 drops of defoaming agent and the balance of deionized water into a container, then slowly adding 3.5g of zinc-aluminum powder and 1.5g of copper powder under the stirring of a heat-collecting constant-temperature heating magnetic stirrer, and adding 0.35g of Mo after the zinc-aluminum powder and the copper powder are wetted 12 Na 3 O 40 P and 0.1g of hydroxyethyl cellulose, and finally stirring for 3 hours until the components are uniformly mixed, thus obtaining the outer layer water-based chromium-free composite coating.
1g of adhesive (AC-66), dispersant (Tween 20 and (CH) 2 OH） 2 ) Adding 0.40g, 1.6g of protective agent, 3-4 drops of defoaming agent and the balance of deionized water into a container, then slowly adding 3.5g of zinc-aluminum powder under the stirring of a heat-collecting constant-temperature heating magnetic stirrer, and adding 0.35g of Mo after the zinc-aluminum powder is wetted 12 Na 3 O 40 P and 0.1g of hydroxyethyl cellulose, and finally stirring for 3 hours until the components are uniformly mixed, thus obtaining the inner-layer water-based chromium-free composite coating.
And (3) grinding the surface of the matrix with sand paper to remove rust, then soaking in alkaline solution for 40 minutes to remove oil, and then cleaning with alcohol and drying for later use.
Dip-coating the substrate into the inner water-based chromium-free composite coating, then throwing out superfluous solution on the surface by rotating the substrate, so that the surface of the prepared coating is uniform, drying at 100 ℃ for 10 minutes, sintering at 280 ℃ for 30 minutes, and cooling at room temperature to obtain the substrate coated with the inner water-based chromium-free composite coating.
Then, the substrate coated with the inner water-based chromium-free composite coating is dip-coated into the outer water-based chromium-free composite coating, and then the surface redundant solution is thrown out by rotating the substrate, so that the surface of the prepared coating is uniform, and then the substrate is dried at 100 ℃ for 10 minutes, sintered at 280 ℃ for 30 minutes, and cooled at room temperature, so that the final substrate coated with the water-based chromium-free composite coating is obtained.
Example 2
Taking 2g of adhesive (AC-66), dispersant (Tween 20 and (CH) 2 OH） 2 ) Adding 0.40g of protective agent 1.6g, 3-4 drops of defoaming agent and the balance of deionized water into a container, then slowly adding 3.5g of zinc-aluminum powder and 1.5g of copper powder under the stirring of a heat-collecting constant-temperature heating magnetic stirrer, and adding 0.35g of Mo after the zinc-aluminum powder and the copper powder are wetted 12 Na 3 O 40 P and 0.1g of hydroxyethyl cellulose, and finally stirring for 3 hours until the components are uniformly mixed to obtainAn outer layer water-based chromium-free composite coating.
Taking 2g of adhesive (AC-66), dispersant (Tween 20 and (CH) 2 OH） 2 ) Adding 0.40g, 1.6g of protective agent, 3-4 drops of defoaming agent and the balance of deionized water into a container, then slowly adding 3.5g of zinc-aluminum powder under the stirring of a heat-collecting constant-temperature heating magnetic stirrer, and adding 0.35g of Mo after the zinc-aluminum powder is wetted 12 Na 3 O 40 P and 0.1g of hydroxyethyl cellulose, and finally stirring for 3 hours until the components are uniformly mixed, thus obtaining the inner-layer water-based chromium-free composite coating.
And (3) grinding the surface of the matrix with sand paper to remove rust, then soaking in alkaline solution for 40 minutes to remove oil, and then cleaning with alcohol and drying for later use.
Dip-coating the substrate into the inner water-based chromium-free composite coating, then throwing out superfluous solution on the surface by rotating the substrate, so that the surface of the prepared coating is uniform, drying at 100 ℃ for 10 minutes, sintering at 280 ℃ for 30 minutes, and cooling at room temperature to obtain the substrate coated with the inner water-based chromium-free composite coating.
Then, the substrate coated with the inner water-based chromium-free composite coating is dip-coated into the outer water-based chromium-free composite coating, and then the surface redundant solution is thrown out by rotating the substrate, so that the surface of the prepared coating is uniform, and then the substrate is dried at 100 ℃ for 10 minutes, sintered at 280 ℃ for 30 minutes, and cooled at room temperature, so that the final substrate coated with the water-based chromium-free composite coating is obtained.
Example 3
4g of adhesive (AC-66), dispersant (Tween 20 and (CH) 2 OH） 2 ) Adding 0.40g of protective agent 1.6g, 3-4 drops of defoaming agent and the balance of deionized water into a container, then slowly adding 3.5g of zinc-aluminum powder and 1.5g of copper powder under the stirring of a heat-collecting constant-temperature heating magnetic stirrer, and adding 0.35g of Mo after the zinc-aluminum powder and the copper powder are wetted 12 Na 3 O 40 P and 0.1g of hydroxyethyl cellulose, and finally stirring for 3 hours until the components are uniformly mixed, thus obtaining the outer layer water-based chromium-free composite coating.
Taking out adhesive (AC-66) 4g. Dispersing agent (Tween 20 and (CH) 2 OH） 2 ) Adding 0.40g, 1.6g of protective agent, 3-4 drops of defoaming agent and the balance of deionized water into a container, then slowly adding 3.5g of zinc-aluminum powder under the stirring of a heat-collecting constant-temperature heating magnetic stirrer, and adding 0.35g of Mo after the zinc-aluminum powder is wetted 12 Na 3 O 40 P and 0.1g of hydroxyethyl cellulose, and finally stirring for 3 hours until the components are uniformly mixed, thus obtaining the inner-layer water-based chromium-free composite coating.
And (3) grinding the surface of the matrix with sand paper to remove rust, then soaking in alkaline solution for 40 minutes to remove oil, and then cleaning with alcohol and drying for later use.
Dip-coating the substrate into the inner water-based chromium-free composite coating, then throwing out superfluous solution on the surface by rotating the substrate, so that the surface of the prepared coating is uniform, drying at 100 ℃ for 10 minutes, sintering at 280 ℃ for 30 minutes, and cooling at room temperature to obtain the substrate coated with the inner water-based chromium-free composite coating.
Then, the substrate coated with the inner water-based chromium-free composite coating is dip-coated into the outer water-based chromium-free composite coating, and then the surface redundant solution is thrown out by rotating the substrate, so that the surface of the prepared coating is uniform, and then the substrate is dried at 100 ℃ for 10 minutes, sintered at 280 ℃ for 30 minutes, and cooled at room temperature, so that the final substrate coated with the water-based chromium-free composite coating is obtained.
Paint index test analysis
(1) The viscosity of the outer layer aqueous chromium-free composite coating prepared in 3 groups of examples was measured by using a coating-4 cup viscometer, four tests were performed on each coating, and the average value was taken, and the viscosity results of the final measuring coating solutions were examples 1 to 3, respectively: 39S, 37S, 35S. The results prove that the viscosity of the coating liquid is in the normal range.
(2) Fineness test analysis: the fineness test is carried out on the outer layer water-based chromium-free composite coating prepared by 3 groups of examples by using a scraper fineness gauge with international regulation design, the test results are about 15um, the error range is smaller, and the results show that the particles of the coating liquid are smaller, and the uniformity of coating liquid coverage and the compactness of the coating are better.
Coating performance test analysis
(1) Adhesion test: the coating on the substrate surface in 3 groups of examples was tested using a combination of tape and cross-hatch, with all test results being 0, i.e. ISO grade 0, the highest adhesion level.
(2) Thickness test analysis: the electron microscope scanning is carried out on the coating on the surface of the substrate in the 3 groups of embodiments, and the observation shows that the coating is formed by layering metal powder in a scaly shape, the structure is very compact, and the total thickness of the coating is about: example 1 had a thickness of 48um, example 2 had a thickness of 50um, and example 3 had a thickness of 47um.
(3) Appearance test analysis: the coatings of the 3 groups of examples all show grey metallic luster, and the coatings are continuous and smooth and have uniform thickness.
Coating corrosion resistance test analysis
(1) Salt water resistance (5 wt.% NaCl) performance test analysis:
example 1: no obvious rust is generated after 50 days, the surface of the coating is still relatively flat, and no uneven phenomenon is generated; obvious white rust and unevenness appear on the surface of the sample in 100 days, the coating structure is corroded and destroyed by salt water, but no obvious red rust appears, which indicates that the coating has a certain protection effect on the matrix at the moment; after 150 days, large-area red rust appears, the coating is completely destroyed, and the matrix is corroded in a large area.
Example 2: no obvious rust is generated after 50 days, the surface of the coating is still relatively flat, and no uneven phenomenon is generated; obvious white rust and unevenness appear on the surface of the sample in 120 days, the coating structure is corroded and destroyed by salt water, but no obvious red rust appears, which indicates that the coating has a certain protection effect on the matrix at the moment; after 180 days, large-area red rust appears, the coating is completely destroyed, and the substrate is corroded in large area.
Example 3: no obvious rust is generated after 50 days, the surface of the coating is still relatively flat, and no uneven phenomenon is generated; obvious white rust and unevenness appear on the surface of the sample in 110 days, the coating structure is corroded and destroyed by salt water, but no obvious red rust appears, which indicates that the coating has a certain protection effect on the matrix at the moment; after 140 days, large-area red rust appears, the coating is completely destroyed, and the matrix is corroded in a large area.
(2) Electrochemical test analysis: the potentiodynamic polarization curve test was performed on the coated sample piece (as an electrochemical sample piece) after 100 days of brine corrosion and the bare steel sample piece immersed in a 3.5% nacl solution, and the test results showed that the coated sample piece of example 1 after corrosion treatment had a potential of-1.010V, the coated sample piece of example 2 had a potential of-1.016V, and the coated sample piece of example 3 had a potential of-1.012V. While the potential of the Q235 steel was-0.667V, the results of the examples were significantly lower than the substrate potential, indicating that the coating provided cathodic protection to the substrate.
(3) Neutral salt spray test analysis: under the neutral salt spray continuous test, example 1 showed red rust after 95 days, example 2 showed red rust after 100 days, and example 3 showed red rust after 90 days.
(4) SEM surface morphology and CRD phase analysis of composite coating: the special compact surface structure endows the coating with excellent performance and can provide good physical shielding for the substrate. Corrosion products mainly consist of alkaline compounds of zinc and aluminum and copper-chlorine compounds, wherein the copper-chlorine compounds play a role in inhibiting the growth of marine fouling organisms.
The water-based chromium-free composite coating provided by the invention is respectively coated on the surface of a substrate after the inner-layer coating and the outer-layer coating are prepared, compared with a chromium-free zinc-aluminum coating, copper is added to ensure that the fouling resistance is better, and the cost is saved to a great extent because the outer-layer coating only contains copper powder components, and meanwhile, the formed coating is ensured to have enough thickness and corrosion resistance, as shown in a figure 1, the inner layer is mainly in a Zn-AI structure, and the outer layer is mainly in a Cu-Zn-AI structure. Secondly, as can be seen from fig. 2, the coating forms a labyrinth structure, and the labyrinth structure can prolong the penetration path of the corrosive medium to the substrate, thereby further playing a role in shielding the corrosive product, and combining with a sacrificial anode protection mechanism, the corrosive product of the coating is accumulated on the surface of the coating to continuously provide a protection effect for the substrate and inhibit the growth of marine organisms, thereby playing a role in double shielding, and the coating structure of the invention can have excellent comprehensive anti-corrosion performance.
The labyrinth structure can be formed mainly because a proper amount of AC-66 is selected as the adhesive, and after sintering, the multilayer structure of the labyrinth structure can be stacked well under the action of the adhesive, so that the labyrinth structure with multiple loops is formed. Besides, the inner layer and the outer layer are coated, so that the complexity of the labyrinth structure is further increased, and the outer layer coating is coated after the inner layer coating is sintered to form the inner layer coating, and part of the outer layer coating also permeates into the labyrinth structure of the inner layer coating, so that a greater blocking effect on the entry of corrosive media is formed.
In order to make it easier for a person skilled in the art to understand the improvements of the present invention with respect to the prior art, some of the figures and descriptions of the present invention have been simplified, and the above-described embodiments are preferred implementations of the present invention, but in addition, the present invention may be implemented in other ways, and any obvious substitution is within the scope of protection of the present invention without departing from the concept of the present technical solution.

Claims (7)

1. The water-based chromium-free composite coating is characterized by comprising the following raw materials in parts by weight: zinc aluminum powder, an antifouling agent, an adhesive, a corrosion inhibitor, a dispersing agent, a protective agent, a thickening agent, a defoaming agent and deionized water.
2. The water-based chromium-free composite coating according to claim 1, wherein the raw materials comprise the following components in parts by weight:
3.5g of zinc aluminum powder, 1.5g of antifouling agent, 2g of adhesive, 0.35g of corrosion inhibitor, 0.40g of dispersing agent, 1.6g of protective agent, 0.1g of thickening agent, 3-4 drops of defoaming agent and the balance of deionized water;
wherein the antifouling agent is copper powder, the adhesive is AC-66, and the corrosion inhibitor is Mo 12 Na 3 O 40 P, the dispersant is Tween 20 (CH) 2 OH） 2 The thickener is hydroxyethyl cellulose.
3. The method for preparing the aqueous chromium-free composite coating according to claims 1-2, comprising the steps of:
adding a proper amount of adhesive, dispersing agent, protective agent, defoaming agent and deionized water into a container, then slowly adding zinc-aluminum powder and an anti-fouling agent under the stirring of a heat-collecting constant-temperature heating magnetic stirrer, adding a proper amount of corrosion inhibitor and thickener after the zinc-aluminum powder and the anti-fouling agent are wetted, and finally stirring for 2.5-3.5 hours until all the components are uniformly mixed to obtain the outer-layer water-based chromium-free composite coating;
adding a proper amount of adhesive, dispersing agent, protective agent, defoaming agent and deionized water into a container, then slowly adding zinc aluminum powder under the stirring of a heat-collecting constant-temperature heating magnetic stirrer, adding a proper amount of corrosion inhibitor and thickening agent after the zinc aluminum powder is wetted, and finally stirring for 2.5-3.5 hours until all the components are uniformly mixed, thus obtaining the inner-layer water-based chromium-free composite coating.
4. The application method of the water-based chromium-free composite coating, which is prepared by the preparation method of claim 3, is characterized by comprising the following steps:
pretreatment: grinding the surface of the matrix with sand paper to remove rust, then soaking in alkaline solution for 40 minutes to remove oil, then cleaning with alcohol and drying for later use;
primary coating: dip-coating a matrix into the inner-layer water-based chromium-free composite coating, removing redundant solution on the surface of the matrix to ensure that the surface of the prepared coating is uniform, drying and sintering, and cooling at room temperature to obtain the matrix coated with the inner-layer water-based chromium-free composite coating;
and (3) secondary coating: dip-coating the substrate obtained after primary coating into an outer layer water-based chromium-free composite coating, removing redundant solution on the surface of the substrate to ensure that the surface of the prepared coating is uniform, drying and sintering, and cooling at room temperature to obtain the substrate coated with the composite coating.
5. The method for using the water-based chromium-free composite paint according to claim 4, wherein the method comprises the following steps: in both the primary and secondary coating steps, excess solution is thrown off the surface by rotating the substrate.
6. The method for using the water-based chromium-free composite paint according to claim 4, wherein the method comprises the following steps: in the primary coating and the secondary coating steps, the drying and sintering modes are that the pre-drying is carried out for 8-10 minutes, and then the high-temperature sintering is carried out for 25-30 minutes.
7. The method for using the water-based chromium-free composite paint according to claim 6, wherein the method comprises the following steps: the pre-baking temperature is 100 ℃ and the sintering temperature is 280 ℃.
CN202211576614.5A 2022-12-09 2022-12-09 Preparation method and application method of water-based chromium-free composite coating and coating thereof Pending CN116179001A (en)

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Citations (6)

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Publication number Priority date Publication date Assignee Title
US5298059A (en) * 1991-03-29 1994-03-29 Nippon Paint Co., Ltd. Anticorrosive coating composition
CN1232060A (en) * 1998-04-13 1999-10-20 赵全玺 Inorganic phosphate paint
KR20150124213A (en) * 2014-04-28 2015-11-05 코오롱글로텍주식회사 Composition for antistatic coating and fabric of vehicle seat with antistatic and antifouling property
CN106497259A (en) * 2016-10-26 2017-03-15 沈阳理工大学 Aqueous chromium-free Dacroment-fluorubber composite coating and preparation method thereof
CN106893485A (en) * 2017-03-22 2017-06-27 广东工业大学 Relatively low chromium-free zinc aluminum coating of a kind of sintering temperature and its production and use
CN108373608A (en) * 2016-11-18 2018-08-07 中国科学院金属研究所 A kind of environment-friendly water-based chromium-free zinc aluminum conductive coating and its preparation method and application

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5298059A (en) * 1991-03-29 1994-03-29 Nippon Paint Co., Ltd. Anticorrosive coating composition
CN1232060A (en) * 1998-04-13 1999-10-20 赵全玺 Inorganic phosphate paint
KR20150124213A (en) * 2014-04-28 2015-11-05 코오롱글로텍주식회사 Composition for antistatic coating and fabric of vehicle seat with antistatic and antifouling property
CN106497259A (en) * 2016-10-26 2017-03-15 沈阳理工大学 Aqueous chromium-free Dacroment-fluorubber composite coating and preparation method thereof
CN108373608A (en) * 2016-11-18 2018-08-07 中国科学院金属研究所 A kind of environment-friendly water-based chromium-free zinc aluminum conductive coating and its preparation method and application
CN106893485A (en) * 2017-03-22 2017-06-27 广东工业大学 Relatively low chromium-free zinc aluminum coating of a kind of sintering temperature and its production and use

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