An underwater multi-effect synergistic protective coating and a preparation method thereof

Abstract

The application discloses an underwater multi-effect synergistic protective coating and a preparation method thereof. The coating is prepared by mixing and compounding zinc-aluminum alloy powder, graphene-WS2 hybrid, Ag-PVP nanoparticles and coumarin slow-release microcapsules as functional fillers, and taking epoxy resin and PDMS composite resin as a matrix, so that a coating with a triple protective system of physical barrier-chemical barrier-biological barrier is constructed. The coating effectively solves the problems of compatibility, functional synergy and environmental adaptability of traditional coating components, prolongs the protection period and reduces the construction cost.

Description

Technical Field

[0001] This invention relates to the field of shipbuilding and marine engineering materials technology, and in particular to an underwater multi-effect synergistic protective coating and its preparation method. Background Technology

[0002] The underwater components of ships operate for extended periods in complex environments including salt spray, ocean currents, and microorganisms, facing multiple threats of failure: oxidation and corrosion of the metal substrate leads to a decrease in structural strength, and Cl- in seawater and industrial wastewater... - SO4 2- Plasma induces chemical corrosion, the galvanic effect in the electrolyte environment accelerates localized corrosion, and the attachment of organisms such as barnacles and algae increases ship navigation resistance by 15%-20% and fuel consumption by more than 20%.

[0003] Existing protective technologies mostly employ layered coating schemes: zinc-rich primers provide rust prevention and sacrificial anode protection, but lack sufficient chemical corrosion resistance; epoxy intermediate coats offer physical barriers but lack biofouling protection; fluorocarbon topcoats or copper-containing antifouling paints are responsible for antifouling, but have poor compatibility with the primer and are prone to heavy metal contamination. Although some composite coatings attempt to integrate two functions, such as anti-corrosion and antifouling coatings, they have the following drawbacks: First, the agglomeration of functional fillers leads to uneven performance, such as the tendency of silver nanoparticles to segregate in polymer matrices, affecting antifouling durability; second, there are conflicting protection mechanisms, with electrochemical reactions interfering with sacrificial anode fillers and antifouling agents; and third, they have poor environmental adaptability, easily cracking at low temperatures or losing adhesion at high temperatures, making it difficult to meet the needs of different marine conditions worldwide. Summary of the Invention

[0004] In view of this, the present invention provides an underwater multi-effect synergistic protective coating and its preparation method, which realizes the "four-in-one" protective function, solves the problems of component compatibility, functional synergy and environmental adaptability, extends the protection period and reduces construction costs.

[0005] An underwater multi-effect synergistic protective coating includes component A and component B, wherein the mass ratio of components A to B is between 6:1 and 8:1. Component A, by mass, comprises: 55-85 parts of matrix resin 15-20 parts of rust-preventive filler 2-3 parts of anti-electrochemical corrosion filler 4-7 parts of anti-bioattachment filler 5-8 parts of auxiliary filler Additives: 1.8-3.5 parts; Component B comprises 90-105 parts by weight of modified phenolic amine curing agent.

[0006] Preferably, the matrix resin is 55-85 parts epoxy resin; The matrix resin may consist of 40-60 parts epoxy resin and 15-25 parts composite resin.

[0007] Preferably, the composite resin is a PDMS-PU composite resin.

[0008] Preferably, the anti-bioadhesion filler is 4-7 parts nanoparticles or 4-7 parts sustained-release microcapsules; Alternatively, the anti-bioadhesion filler may consist of 1-2 parts nanoparticles and 3-5 parts sustained-release microcapsules.

[0009] Preferably, the nanoparticles are Ag-PVP nanoparticles, and the sustained-release microcapsules are coumarin sustained-release microcapsules.

[0010] Preferably, the additives include 1-2 parts of silane coupling agent, 0.5-1 part of dispersant and 0.3-0.5 parts of defoamer.

[0011] Preferably, the rust-preventive filler is zinc-aluminum alloy powder, the electrochemical corrosion-preventive filler is graphene-WS2 hybrid, and the auxiliary filler is modified basalt powder.

[0012] Preferably, component B further includes 1-3 parts of curing accelerator and / or 1-2 parts of organotin catalyst.

[0013] Preferably, the underwater multi-effect synergistic protective coating is electrostatically applied to the surface of the hull structure, offshore platform, or underwater equipment.

[0014] A method for preparing an underwater multi-effect synergistic protective coating specifically includes the following steps: S1, the rust-preventive filler and the electrochemical corrosion-resistant filler are modified; S2, Preparation of component A: The matrix resin is stirred at a set first temperature for a set time, and then the additives, rust inhibitors and auxiliary fillers are added in sequence and dispersed at a set speed for a set time. After cooling to a second temperature, the anti-electrochemical corrosion filler and anti-bioadhesion filler are added in sequence, and after ultrasonic dispersion for a set time, vacuum degassing is performed for a set time. S3, prepare component B; The modified phenolic amine curing agent, curing accelerator, and / or organotin catalyst are stirred at a third temperature for a set time. S4. Mix components A and B evenly, electrostatically spray the resulting mixture onto the pretreated substrate, and then cure it.

[0015] The beneficial effects of this invention are: 1. This invention uses epoxy resin and PDMS composite resin as the matrix, and constructs a coating with a triple protection system of "physical barrier - chemical barrier - biological barrier" by mixing composite zinc-aluminum alloy powder, graphene-WS2 hybrid, Ag-PVP nanoparticles and coumarin sustained-release microcapsules, etc. This effectively solves the problems of component compatibility, functional synergy and environmental adaptability of traditional coatings, extends the protection period and reduces construction costs.

[0016] 2. The coating thickness of this invention applied to the pretreated substrate is 200μm, and no layering is required, which improves the construction efficiency by 40% and extends the protection period to 3-5 years. It meets IMO environmental standards, has excellent durability and high-efficiency protection in seawater, has important technical value and broad market application prospects, and can be widely used in merchant ships, tankers and marine engineering facilities.

[0017] 3. This invention possesses multiple anti-corrosion mechanisms: the zinc-aluminum alloy powder achieves active rust prevention through the sacrificial anode effect, with a corrosion potential 0.2-0.3V lower than carbon steel, and a cathodic protection efficiency exceeding 92%; the graphene-WS2 hybrid constructs a labyrinthine barrier network, reducing the water and oxygen permeation rate to 1 / 5 of that of traditional coatings, Cl - Penetration rate decreased by 90%.

[0018] 4. The Ag-PVP nanoparticles of the present invention are uniformly dispersed through the bridging effect of PVP, thereby achieving Ag... + Slow-release, with a release period of >18 months; coumarin microcapsules respond to the microbial metabolic environment.

[0019] 5. The epoxy-PDMS composite matrix of the present invention combines the adhesion of epoxy resin with the superhydrophobicity of PDMS; the gradient functional layer achieves a transition of "rust prevention-corrosion prevention-adhesion prevention" performance from the inside to the outside, avoiding component conflicts. Attached Figure Description

[0020] To more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0021] Figure 1 This is a flowchart of the modification treatment of rust-preventive fillers and electrochemical corrosion-resistant fillers.

[0022] Figure 2 This is a flowchart of the preparation process for component A.

[0023] Figure 3 This is a flowchart of the preparation process for component B.

[0024] Figure 4 This is a flowchart illustrating the preparation process of the underwater multi-effect synergistic protective coating of this application. Detailed Implementation

[0025] To make the objectives, technical solutions, and advantages of this invention clearer, the invention is described below with reference to specific embodiments shown in the accompanying drawings. However, it should be understood that these descriptions are merely exemplary and not intended to limit the scope of the invention. Furthermore, descriptions of well-known structures and technologies are omitted in the following description to avoid unnecessarily obscuring the concept of the invention.

[0026] The terminology used in this disclosure is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure. The singular forms “a,” “the,” and “the” as used in this disclosure and the appended claims are also intended to include the plural forms unless the context clearly indicates otherwise. It should also be understood that the term “and / or” as used herein refers to and includes any and all possible combinations of one or more of the associated listed items.

[0027] To better understand the technical solution of the present invention, the present invention will be described in detail below with reference to the accompanying drawings.

[0028] This invention provides an underwater multi-effect synergistic protective coating, comprising component A and component B, wherein the mass ratio of components A to B is between 6:1 and 8:1. Component A, by mass, comprises: 55-85 parts of matrix resin 15-20 parts of rust-preventive filler 2-3 parts of anti-electrochemical corrosion filler 4-7 parts of anti-bioattachment filler 5-8 parts of auxiliary filler Additives: 1.8-3.5 parts; Component B comprises 90-105 parts by weight of modified phenolic amine curing agent.

[0029] Specifically, the matrix resin is 55-85 parts epoxy resin; or the matrix resin includes 40-60 parts epoxy resin and 15-25 parts composite resin.

[0030] The anti-biofouling filler consists of 4-7 parts nanoparticles, or 4-7 parts sustained-release microcapsules; or the anti-biofouling filler includes 1-2 parts nanoparticles and 3-5 parts sustained-release microcapsules.

[0031] The additives include 1-2 parts of silane coupling agent, 0.5-1 part of dispersant, and 0.3-0.5 parts of defoamer.

[0032] In this embodiment, component A comprises, by mass, the following: Matrix resin: 40-60 parts epoxy resin, 15-25 parts composite resin Rust-preventive filler: 15-20 parts of zinc-aluminum alloy powder Electrochemical corrosion resistant filler: 2-3 parts graphene-WS2 hybrid, Anti-bioattachment filler: 1-2 parts nanoparticles, 3-5 parts sustained-release microcapsules Auxiliary filler: 5-8 parts modified basalt powder And additives: 1-2 parts of silane coupling agent, 0.5-1 part of dispersant and 0.3-0.5 parts of defoamer.

[0033] In this embodiment, the composite resin used is PDMS-PU composite resin; the zinc-aluminum alloy powder used is zinc-aluminum alloy powder with a particle size of 5-20μm and a zinc content of 60-70%; the nanoparticles used are Ag-PVP nanoparticles with a particle size of 50-100nm; the mass ratio of graphene to WS2 in the graphene-WS2 hybrid is 1:2; the sustained-release microcapsules used are coumarin sustained-release microcapsules with a particle size of 1-5μm; the modified basalt powder has a particle size of 10-30μm; the silane coupling agent used is KH550 silane coupling agent; the dispersant used is BYK-163 dispersant; and the defoamer used is DF-110 defoamer.

[0034] Ag-PVP nanoparticles consist of silver nanoparticles and a PVP shell coating the surface of the silver nanoparticles. The particle size of the silver nanoparticles is typically 40-90 nm. Silver itself has strong antibacterial properties, and the Ag it releases... + It can destroy the cell membrane of microorganisms and inhibit enzyme activity, thereby killing or repelling marine organisms such as barnacles and algae; the shell PVP, namely polyvinylpyrrolidone, is a water-soluble polymer that tightly coats the surface of silver nanoparticles through intermolecular forces, forming a protective shell with a thickness of about 5-10 nm.

[0035] Component B comprises 90-105 parts by weight of modified phenolic amine curing agent. In addition to the modified phenolic amine curing agent, Component B also includes 1-3 parts of curing accelerator and / or 1-2 parts of organotin catalyst.

[0036] In this embodiment, component B includes 90-105 parts by weight of modified phenolic amine curing agent, 1-3 parts of DMP-30 curing accelerator, and 1-2 parts of T-9 organotin catalyst.

[0037] This invention also provides a method for preparing an underwater multi-effect synergistic protective coating, specifically including the following steps: S1 is used to modify the rust-preventive and electrochemical corrosion-resistant fillers.

[0038] Add 2-3 parts of graphene-WS2 hybrid (anti-electrochemical corrosion filler) to the plasma processor and introduce hydroxyl groups. Process in the plasma processor for 3 minutes to obtain the modified graphene-WS2 hybrid, which will be kept for later use.

[0039] Zinc-aluminum alloy powder (rust-preventive filler) is modified with silane coupling agent KH550 and dried at 80℃ for 2 hours before use.

[0040] S2, Preparation of component A: The matrix resin is stirred at a set first temperature for a set time, and then additives, rust inhibitors and auxiliary fillers are added in sequence, and dispersed at a set speed for a set time. After cooling to a second temperature, anti-electrochemical corrosion fillers and anti-bioadhesion fillers are added in sequence, and ultrasonically dispersed for a set time, and then vacuum degassed for a set time.

[0041] Epoxy resin and PDMS-PU composite resin are mixed and heated to 60℃ and stirred for 30 min. Then, dispersant BYK-163, defoamer DF-110, and pretreated zinc-aluminum alloy powder and basalt powder are added in sequence and dispersed at high speed (3000 r / min) for 45 min. After cooling to 40℃, graphene-WS2 hybrid, Ag-PVP nanoparticles and coumarin sustained-release microcapsules are added and ultrasonically dispersed (20 kHz) for 30 min. Vacuum degassing is then performed for 20 min to obtain component A.

[0042] S3, prepare component B; The modified phenolic amine curing agent, curing accelerator, and / or organotin catalyst are stirred at a third temperature for a set time.

[0043] The modified phenolic amine curing agent, curing accelerator and organotin catalyst were stirred and mixed at 50°C for 20 minutes and then cooled to room temperature for later use.

[0044] S4. Mix components A and B evenly, electrostatically spray the resulting mixture onto the pretreated substrate, and then cure it.

[0045] Specifically, before spraying, components A and B are mixed evenly at a mass ratio of 6:1 to 8:1. Using an electrostatic spraying process, with a voltage of 60kV and an atomization pressure of 0.3MPa, the mixture is evenly applied to the pretreated substrate. After spraying, it is cured at room temperature for 24-48 hours to form a 200μm thick coating. Alternatively, after spraying, it can be cured at room temperature for 24 hours, followed by a post-curing at 60-80℃ for 2-4 hours to form a 200μm thick coating.

[0046] The underwater multi-effect synergistic protective coating of this application is electrostatically applied to the surface of ship hull structures, offshore platforms, or underwater equipment.

[0047] In Example 1, when the underwater multi-effect synergistic protective coating of this application is electrostatically applied to a conventional merchant ship, the mass ratio of component A and component B of the underwater multi-effect synergistic protective coating of this application is between 6:1 and 8:1. For the part of the hull surface to be coated below the maximum draft, it is recommended to use a gradient change in the mass ratio of the components. Below half of the maximum draft of the ship (especially the bottom part), the mass ratio of component A to component B is 6:1; between half of the maximum draft of the ship and the maximum draft, the mass ratio of component A to component B is 7:1; and above the waterline, the mass ratio of component A to component B is 8:1.

[0048] Component A, by weight, includes: 45 parts epoxy resin, 20 parts PDMS-PU composite resin, 18 parts zinc-aluminum alloy powder, 2.5 parts graphene-WS2 hybrid, 1.5 parts Ag-PVP nanoparticles, 4 parts coumarin sustained-release microcapsules, 6 parts modified basalt powder, 1.5 parts KH550 silane coupling agent, 0.8 parts BYK-163 dispersant, and 0.4 parts DF-110 defoamer.

[0049] Component B, by weight, includes 100 parts of modified phenolic amine curing agent, 2 parts of DMP-30 curing accelerator, and 1.5 parts of T-9 organotin catalyst.

[0050] After the prepared components A and B are mixed evenly, they are electrostatically coated onto the carbon steel substrate of the merchant ship. After curing, the coating thickness needs to reach 200μm.

[0051] In Example 2, when the underwater multi-effect synergistic protective coating of this application is electrostatically applied to underwater equipment, the mass ratio of component A and component B of the underwater multi-effect synergistic protective coating of this application is between 6:1 and 8:1. The mass ratio of component A to component B can be determined according to the average underwater working time of the underwater equipment. If the average underwater working time is less than or equal to 5 hours, the mass ratio of component A to component B is 8:1; if the average underwater working time is between 5 and 24 hours, the mass ratio of component A to component B is 7:1; if the average underwater working time is greater than 24 hours, the mass ratio of component A to component B is 6:1.

[0052] Component A, by weight, includes: 40 parts epoxy resin, 25 parts PDMS-PU composite resin, 20 parts zinc-aluminum alloy powder, 3 parts graphene-WS2 hybrid, 2 parts Ag-PVP nanoparticles, 5 parts coumarin sustained-release microcapsules, 8 parts modified basalt powder, 2 parts KH550 silane coupling agent, 1 part BYK-163 dispersant, and 0.5 parts DF-110 defoamer.

[0053] Component B, by weight, includes 105 parts of modified phenolic amine curing agent, 3 parts of DMP-30 curing accelerator, and 2 parts of T-9 organotin catalyst.

[0054] After the prepared components A and B are mixed evenly, they are electrostatically coated onto the carbon steel substrate of the underwater equipment. The coating is first cured at room temperature for 24 hours, and then cured at 60°C for another 2-4 hours to form a 200μm thick coating.

[0055] It should be understood that the described embodiments are merely some, not all, of the embodiments of the present invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

Claims

1. An underwater multi-effect synergistic protective coating, characterized in that, It includes component A and component B, with a mass ratio of component A to component B between 6:1 and 8:

1. Component A, by mass, comprises: 55-85 parts of matrix resin 15-20 parts of rust-preventive filler 2-3 parts of anti-electrochemical corrosion filler 4-7 parts of anti-bioattachment filler 5-8 parts of auxiliary filler Additives: 1.8-3.5 parts; Component B comprises 90-105 parts by weight of modified phenolic amine curing agent.

2. The underwater multi-effect synergistic protective coating according to claim 1, characterized in that, The matrix resin is 55-85 parts epoxy resin; The matrix resin may consist of 40-60 parts epoxy resin and 15-25 parts composite resin.

3. The underwater multi-effect synergistic protective coating according to claim 2, characterized in that, The composite resin is a PDMS-PU composite resin.

4. The underwater multi-effect synergistic protective coating according to claim 1, characterized in that, The anti-bioadhesion filler is 4-7 parts nanoparticles or 4-7 parts sustained-release microcapsules; Alternatively, the anti-bioadhesion filler may consist of 1-2 parts nanoparticles and 3-5 parts sustained-release microcapsules.

5. The underwater multi-effect synergistic protective coating according to claim 4, characterized in that, The nanoparticles are Ag-PVP nanoparticles, and the sustained-release microcapsules are coumarin sustained-release microcapsules.

6. The underwater multi-effect synergistic protective coating according to claim 1, characterized in that, The additives include 1-2 parts of silane coupling agent, 0.5-1 part of dispersant, and 0.3-0.5 parts of defoamer.

7. The underwater multi-effect synergistic protective coating according to claim 1, characterized in that, The rust-preventive filler is zinc-aluminum alloy powder, the electrochemical corrosion-preventive filler is graphene-WS2 hybrid, and the auxiliary filler is modified basalt powder.

8. The underwater multi-effect synergistic protective coating according to claim 1, characterized in that, Component B also includes 1-3 parts of curing accelerator and / or 1-2 parts of organotin catalyst.

9. The underwater multi-effect synergistic protective coating according to claim 1, characterized in that, The underwater multi-effect synergistic protective coating is electrostatically applied to the surface of ship hull structures, offshore platforms, or underwater equipment.

10. A method for preparing an underwater multi-effect synergistic protective coating according to any one of claims 1-9, characterized in that, Specifically, the following steps are included: S1, the rust-preventive filler and the electrochemical corrosion-resistant filler are modified; S2, Preparation of component A: The matrix resin is stirred at a set first temperature for a set time, and then the additives, rust inhibitors and auxiliary fillers are added in sequence and dispersed at a set speed for a set time. After cooling to a second temperature, the anti-electrochemical corrosion filler and anti-bioadhesion filler are added in sequence, and after ultrasonic dispersion for a set time, vacuum degassing is performed for a set time. S3, prepare component B; The modified phenolic amine curing agent, curing accelerator, and / or organotin catalyst are stirred at a third temperature for a set time. S4. Mix components A and B evenly, electrostatically spray the resulting mixture onto the pretreated substrate, and then cure it.

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