Self-layering coating

Abstract

To provide: a self-multilayered anticorrosive coating; and an accompanying method of self-multilayered anticorrosive coating on a base material.SOLUTION: A self-multilayered anticorrosive coating includes: sacrificial metal particles; a graphite material; at least two different monomers or polymers; silane selected from the group consisting of alkoxysilane, dialkoxysilane, trialkoxysilane, and tetraalkoxysilane; and a material that prevents polymerization of at least one kind of monomer in the interior of the coating.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a self-layering anticorrosion coating. [Background technology]

[0002] Self-layering coatings are typically made from immiscible or poorly miscible components that are mixed with the aid of a solvent. Thermodynamics is the driving force for the separation of the components after some or all of the solvent has evaporated. Even if phase separation occurs to form a layered structure, there is no guarantee that the primer will adhere to the substrate. Instead, the topcoat may separate into two layers, one in contact with the substrate and the other on top. This is undesirable if cathodic protection (galvanic protection) is to be used, as the electrically insulating layer on the substrate would prevent cathodic protection (cathodic protection).

[0003] Surface free energy differences may also be used to drive phase separation. Zinc-rich primers are composed of high surface energy resins such as epoxies or urethanes. Topcoats are composed of low surface resins that favor layering. These resins may contain silicone or fluorine functional groups to enhance layering. Examples include amine- or epoxy-functional polysiloxanes, silicone-modified alkyls, fluoroethylene vinyl ether resins, and seed oils.

[0004] Anticorrosion coatings place further requirements on self-layering systems. In the best case, the primer should provide cathodic protection. Traditionally, cathodic protection is achieved by incorporating sacrificial metal particles, such as zinc, magnesium, or aluminum particles, which can interfere with phase separation. Even partial separation of the topcoat on the surface of the substrate would likely destroy cathodic protection, as the electrical connection between the sacrificial metal particles and the substrate would be lost. Summary of the Invention [Means for solving the problem]

[0005] The present teachings solve all of these problems. The primer is advantageously a zinc-rich epoxy, and the polymer matrix is ​​made conductive with graphitic materials such as carbon nanotubes (CNTs) or graphene. The topcoat is a moisture-curing siloxane. Siloxane monomers have low viscosity and may be used as a solvent for the primer in addition to other solvents. Water is excluded from the interior of the coating after application, and siloxane polymerization may occur only at the coating-air interface due to moisture in the air. This results in separation of the primer and topcoat. [Brief explanation of the drawings]

[0006] The present teachings will now be described with reference to the accompanying drawings.

[0007] [Figure 1] FIG. 1 shows the formation of siloxanes. [Figure 2A] FIG. 2A shows the cleavage of an oxazolidine. [Figure 2B] FIG. 2B shows a dimeric oxazolidine. [Figure 3A] FIG. 3A shows a schematic diagram of a dye incorporated into a siloxane layer. [Figure 3B] FIG. 3B shows a schematic diagram of a dye incorporated into a siloxane layer. [Figure 4A] FIG. 4A shows an IR overlay of a UV-curable self-layering system, with the top spectrum being the air-coating interface and the bottom spectrum being the substrate-coating interface. [Figure 4B] FIG. 4B shows an IR overlay of the UV-curable self-layering system, where the top spectrum is the photoinitiator and vinyl ether mixture after UV curing and the bottom spectrum is the air-coating interface. [Figure 4C] FIG. 4C shows an IR overlay of a UV-curable self-layering system, with the top spectrum being bisphenol A diglycidyl ether and the bottom spectrum being the substrate-coating interface. DETAILED DESCRIPTION OF THE INVENTION

[0008] definition Self-layering coating: A single coating material that is a mixture of at least two different materials can be applied to a surface using a single process, and after application, the components form two or more layers.

[0009] Primer layer or bottom layer: The coating layer in contact with the substrate.

[0010] Topcoat layer or uppermost layer: The coating layer that is in direct contact with air.

[0011] External Effector: A chemical or physical agent external to the coating that induces hardening of the monomer after application. The external effector may be a common hardener such as water, an amine, or a physical agent such as electromagnetic radiation.

[0012] Detailed Description Figure 1 depicts dimethoxysilane, which has two other moieties attached to the silicon. These may be alkyl or aryl groups, or may contain functional groups such as alkoxy, carbonyl, epoxy, or amino groups. Alkoxysilanes, dialkoxysilanes, trialkoxysilanes, or tetraalkoxysilanes may also be used. Trialkoxysilanes and tetraalkoxysilanes result in crosslinking, giving a more glass-like coating. The methoxy groups are easily hydrolyzed. The resulting silicic acid derivative spontaneously polymerizes, releasing some of the water used in the first step. However, more water is required to complete this process. In the present teachings, the water is derived from humid air. Thus, in this embodiment, water is the external effector.

[0013] In one embodiment of the present teachings, the monomer in the primer is an epoxy cured by an amine. Many other curing agents are possible, including thiols, phenols, and carboxylic acid anhydrides. The curing of the epoxy does not interfere with the curing of the siloxane, and vice versa. To ensure bonding between the primer and the topcoat, some aminoalkyldialkoxysilane or aminoalkyltrialkoxysilane may be added to the mixture. The amino group bonds with the epoxy, and the dimethoxysilane bonds with the siloxane layer.

[0014] Some water scavengers are added to prevent siloxane formation within the coating. Water may be present on the surface of the substrate, which can lead to significant siloxane formation. Industrial epoxies may also contain small amounts of water. Therefore, siloxanes may be uniformly formed within the coating. Liquid and solid water scavengers may be added to suppress siloxane formation. Liquid scavengers effectively remove water from the surface of the substrate. However, they may also remove water from the air interface too effectively. Therefore, only relatively small amounts of liquid water scavengers are used unless the substrate is wet. Solid water scavengers, such as molecular sieves, silica, and many metal salts and oxides, do not move much within the coating, keeping it dry. Combining liquid and solid water scavengers prevents siloxane polymerization at the metal-coating interface and within the coating. Polymerization may occur only at the air interface. This results in auto-separation of the primer and topcoat. This process may be further enhanced by selecting monomers that do not mix well with each other. Mixing only occurs during manufacturing because an appropriate solvent is used, resulting in a homogeneous product.

[0015] Oxazolidines are an example of liquid water scavengers (Figure 2A). Water cleaves the double bond, releasing a primary amino group, which can react with the epoxy, which can be detrimental. However, dimeric oxazolidines (Figure 2B) can act as curing agents for the epoxy, forming diamines that may be beneficial.

[0016] In another embodiment of the present teachings, an epoxy primer and a polyurea topcoat can also be used. In this case, an epoxy monomer and a diisocyanate are mixed, and a corrosion-protective component is added. A dimeric oxazolidine is added in sufficient quantity so that, after hydrolysis, the diamine formed from the dimeric oxazolidine cures both the diisocyanate and the epoxy. The diamine chemically bonds to the epoxy. The hydrolysis reaction occurs at the air coating surface; the diisocyanate reacts much faster than the epoxy, and a urea polymer forms at the interface. The diisocyanate molecules diffuse near the surface and become trapped there. Zinc and other micron-sized particles migrate very slowly and remain primarily in the epoxy layer, as desired. If molecular dyes are used, they may also diffuse near the surface. Once all the diisocyanate is consumed, the primer cures.

[0017] It is generally agreed that to obtain effective cathodic protection, the concentration of sacrificial metal particles should be greater than 50% by weight, usually greater than 70% by weight. These limits may be lower if the polymer matrix is ​​a conductive polymer. The sacrificial metal particles may consist primarily of roughly spherical particles (the roughly spherical shape includes microscopic irregular surface structures). However, some of the sacrificial particles may have a flake-like structure. This increases electrical conductivity and electrolytic (galvanic) activity.

[0018] Sacrificial particles may, in principle, be made from any metal with a more positive redox potential than iron. Most positive ones, such as alkali metals, react too quickly with oxygen and water to be practical. Commonly used sacrificial metals include zinc, magnesium, and aluminum. Some alloys, including zinc / magnesium alloys, can be used.

[0019] In another embodiment of the present teachings, approximately 20% by weight of Zn flakes are used to create a mirror effect that prevents light from penetrating the lower half of the coating. Similarly, approximately 1% by weight of CNTs can be estimated to confine light to the upper half of the coating. Approximately 10-30% by weight of Zn flakes and approximately 0.5-2.0% by weight of a CNT / graphene combination can be used. The mirror effect allows light to travel twice through the top layer, and therefore, cure is faster than with absorbing particles.

[0020] In another embodiment of the present teachings, a primer monomer or polymer is utilized in the composition to provide barrier properties. In one embodiment, the primer monomer or polymer in the composition comprises greater than about 15% by weight, and in another embodiment, greater than about 20% by weight. Epoxy resins can be used in the present teachings. The topcoat monomer or polymer can be about 10% to about 20% by weight of the composition.

[0021] The conductive material may be a graphitic material such as carbon nanotubes or graphene, which may have many forms. For example, CNTs may be single-walled (SWNTs), double-walled (DWNTs), or multi-walled (MWNTs). Graphene may be single-walled (single-sheet), double-walled (double-sheet), or multi-walled (multi-sheet). A mixture of CNTs and graphene may also be used. The amount of graphitic material may be about 0.1 to 2% by weight of the primer polymer.

[0022] A dye may be added to the mixture. The dye typically has many functional groups that may bond with the silane, resulting in the dye chemically bonding to the topcoat. In Figure 3, a schematic diagram depicts how the carboxyl group of the dye may be linked to the amino group that is part of the silane. Many different reactive dyes are commercially available. While most were developed for textiles, many are applicable to the self-stratifying coatings of the present teachings.

[0023] Graphite materials absorb electromagnetic radiation, which allows for photoinduced self-layering. When the topcoat is made of a photopolymerizable material, polymerization occurs on the surface only when the coating is irradiated after application. Because graphite materials reflect or absorb radiation, electromagnetic energy does not penetrate the coating before drying. In addition, sacrificial metal particles, particularly flakes, reflect electromagnetic radiation. Therefore, the topcoat automatically forms only on the surface when the monomer diffuses into the surface layer. In one embodiment of the present teachings, the external effector is a photon. Suitable monomers and resins that can be used in the radiation-curable composition include those with functional groups such as acrylate, methacrylate, vinyl ether, cycloaliphatic epoxide, oxetane, or epoxide.

[0024] For radiation curing, a suitable photoinitiator is required to initiate the radiation curing mechanism. UV or visible light photoinitiators can be used. The choice of photoinitiator depends on the functionality of the polymerizable group (i.e., whether the system cures via a free radical or cationic process). In one embodiment of the present teachings, a suitable photoinitiator is one that initiates polymerization upon exposure to radiation from about 200 nm to about 700 nm. Suitable photoinitiators include, for example, 1-hydroxycyclohexylphenylketone, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone, 2,2-dimethoxy-2-phenylacetophenone, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, triphenylsulfonium triflate, triarylsulfonium hexafluoroantimonate salts, and triarylsulfonium hexafluorophosphate salts. These can be used alone or in combination with each other. The combination is useful for achieving adequate surface and through cure.

[0025] Photoinitiators that initiate polymerization at visible light wavelengths can be used in field applications. These include those that absorb from about 380 nm to about 740 nm. Suitable photoinitiators of this type include, for example, bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, 5,7-diiodo-3-butoxy-6-fluorone, 2,4,5,7-tetraiodo-3-hydroxy-6-fluorone, and 2,4,5,7-tetraiodo-3-hydroxy-9-cyano-6-fluorone.

[0026] While the present teachings provide separated layers, this separation does not have to be 100%. The lack of complete separation can provide additional adhesion between the layers. As shown in Figures 4A-4C, the primer layer is almost pure epoxy, while the topcoat has little or no epoxy. [Example]

[0027] Example 1. The primer consisted of 181 g of Epon™ 828 (neat, clear, difunctional bisphenol A / epichlorohydrin-derived liquid epoxy resin), 121 g of a 2.9% MWNT dispersion in Aromatic 100 (solvent naphtha), 18 g of t-butyl acetate, 4.1 g of Disparlon™ 6500 (a non-reactive polyamide thixotrope), 1.2 g of Thixotrol™ ST (a rheological additive that is a modified derivative of castor oil), 423 g of UP#6 zinc powder, 212 g of zinc flake, 54 g of Zn / Mg alloy, 54 g of epoxidized glass flake, 32 g of Aromatic 100, 1.2 g of phenyltrimethoxysilane, and 2 g of glycidoxypropyltriethoxysilane.

[0028] To 90 g of the primer mixture from the previous paragraph, 10 g of 4 Å molecular sieve powder (Sylosiv™ 4A, GraceDavison) was added. A silane stock mixture was prepared by mixing 16 g of dimethyldimethoxysilane, 4 g of phenyltrimethoxysilane, and 2 g of aminopropyltrimethoxysilane, and 10 g of this mixture was added to 100 g of primer mixture. 1 g of Ancamide™ 2767 (a high-performance modified polyamide hardener) was added to this 10 g primer mixture, and a 5 mil film was spread onto a polypropylene sheet using a drawdown bar. The coating was allowed to cure at ambient temperature for 1 week. The coating was removed from the polypropylene sheet, and IR spectra were recorded at several spots on the top and bottom surfaces (Figures 4A-4C). The spectra from the same side were identical but different from each other. The IR spectra reveal that there was very little epoxy on the top and almost only epoxy on the bottom. Thus, self-layering had occurred.

[0029] Example 2. The primer consisted of 181 g of Epon™ 828, 121 g of a 2.9% MWNT dispersion in Aromatic 100, 18 g of t-butyl acetate, 4.1 g of Disparlon™ 6500, 1.2 g of Thixotrol™ ST, 423 g of UP#6 zinc powder, 212 g of zinc flake, 54 g of Zn / Mg alloy, 54 g of epoxidized glass flake, 32 g of Aromatic 100, 1.2 g of phenyltrimethoxysilane, and 2 g of glycidoxypropyltriethoxysilane.

[0030] To the above primer was added 30 g of triethylene glycol divinyl ether, 3 g of diethylene glycol monovinyl ether, and 0.3 g of triarylsulfonium hexafluorophosphate salt in propylene carbonate (50 wt%). A portion (10 g) of this mixture was mixed with 1 g of Ancamide™ 2767 and cast onto a polypropylene sheet using a 5-mil drawdown bar. After 4 hours, the film was exposed to high-intensity UV radiation using a UV spot curing system. The sample was exposed to radiation for 1 minute, with the light source 10 cm away from the sample.

[0031] The present teachings allow for a single spray of material. The primer and topcoat are mixed, and then the two separate upon contact to form two layers. Typically, the mixture is immiscible, but a solvent is used to make it miscible. In one embodiment of the present teachings, the topcoat is a water-soluble topcoat, which can be achieved using a siloxane. In one embodiment of the present teachings, the silane is hydrolyzed to produce silicic acid, which then spontaneously polymerizes to form siloxane. The hydrolysis of the silane can be triggered by humidity in the ambient air. The coating can be made from a combination of monomers or a combination of monomers and polymers.

[0032] In another embodiment of the present teachings, no insulating layer is used. Molecular sieves can be used to act as a porous material that only allows water to pass through. Other molecules cannot penetrate. The molecular sieves can remove water from the interior of the coating and can also remove water from the metal substrate. No polymerization occurs on the metal substrate. In another embodiment, diamino groups can be used as a hardener for the epoxy. This hardener can be added to the coating by the customer. The epoxy typically polymerizes within a few hours.

[0033] In another aspect of the present teachings, sunlight can be used to induce polymerization, however, sunlight does not completely penetrate the coating due to the black carbon nanotubes as well as the sacrificial metal flakes, which reflect light.

[0034] In another aspect of the present teachings, the application of a self-layering coating can be preceded by the following method: a method of coating an associated substrate with an anticorrosion coating, the method comprising: applying (applying, providing) a first curable liquid layer to the associated substrate, the first curable liquid layer having a thickness of at least about 100 micrometers, the first curable layer comprising at least one polymer or at least one monomer, quasi-one-dimensional or quasi-two-dimensional particles, sacrificial metal particles, and a solvent, wherein a percolation threshold of the quasi-one-dimensional or quasi-two-dimensional particles is not reached in the presence of the solvent, and the percolation threshold of the quasi-one-dimensional or quasi-two-dimensional particles is reached when about 1% to about 20% of the solvent has evaporated; and applying a second curable liquid layer having a thickness of at least 100 micrometers over the first curable liquid layer after the percolation threshold of the quasi-one-dimensional or quasi-two-dimensional particles has been reached and the viscosity of the first curable liquid layer has increased by more than 50%. Following the above method, a self-layering coating can then be applied, thereby creating three separate layers.

[0035] Clause 1 - A self-layering corrosion-protective coating includes a zinc-rich epoxy, a curing agent selected from the group consisting of amines, thiols, phenols, and carboxylic acid anhydrides, a binder selected from the group consisting of aminoalkyldialkoxysilanes, dimethoxysilanes, and aminoalkyltrialkoxysilanes, a graphite material, a solvent, and a water scavenger.

[0036] Clause 2 - The self-layering corrosion-protective coating comprises sacrificial metal particles, a graphite material, a first monomer, at least a second monomer or at least a first polymer, and a material that prevents polymerization of at least one of the monomers within the coating.

[0037] Clause 3 - The coating of clause 2, further comprising a curing agent and a binder.

[0038] Clause 4 - The coating of clause 2 or clause 3, wherein the at least two different monomers or polymers are selected from the group consisting of epoxies, polyurethanes, acrylates, methacrylates, vinyl ethers, cycloaliphatic epoxides, oxetanes, epoxides, photopolymers, siloxanes, and polyureas.

[0039] Clause 5 - The coating of any one of clauses 2 to 4, wherein the graphite material is selected from the group consisting of single-walled carbon nanotubes, double-walled carbon nanotubes, multi-walled carbon nanotubes, single-walled graphene, bi-walled graphene, or multi-walled graphene.

[0040] Clause 6 - The coating of any one of clauses 2 to 5, wherein the material that prevents polymerization of at least one monomer within the coating is a water scavenger selected from the group consisting of liquid water scavengers, molecular sieves, silica, metal salts, and metal oxides.

[0041] Clause 7 - The coating of any one of clauses 2 to 6, wherein the sacrificial metal particles are selected from the group consisting of any metal having a more positive redox potential than iron.

[0042] Clause 8 - The coating of any one of clauses 2 to 7, wherein the sacrificial metal particles are selected from the group consisting of zinc, magnesium, aluminum, and alloys thereof.

[0043] Clause 9 - The coating of any one of clauses 2 to 8, wherein the curing agent is selected from the group consisting of amines, thiols, phenols, and carboxylic acid anhydrides, and the coupling agent is selected from the group consisting of silanes having at least two alkyl groups, non-limiting examples being aminoalkyldialkoxysilanes, dimethoxysilanes, and aminoalkyltrialkoxysilanes.

[0044] Clause 10 - The coating is not a mixture of 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone, 2,2-dimethoxy-2-phenylacetophenone, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, triphenylsulfonium triflate, triarylsulfonium hexafluoroantimonate salts, triarylsulfonium hexafluorophosphine 10. The coating of any one of clauses 2 to 9, further comprising a photoinitiator selected from the group consisting of a bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium salt, bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, 5,7-diiodo-3-butoxy-6-fluorone, 2,4,5,7-tetraiodo-3-hydroxy-6-fluorone, and 2,4,5,7-tetraiodo-3-hydroxy-9-cyano-6-fluorone.

[0045] Clause 11 - A method of self-layering anticorrosive coating on an associated substrate, comprising the steps of mixing together a monomer or polymer, a solvent, a graphite material, and sacrificial metal particles; adding a material that prevents polymerization within said coating before and immediately after application onto said associated substrate; and adding a silane mixture.

[0046] Clause 12 - The method of clause 11, further comprising the steps of adding a curing agent and applying a mixture of the monomer or polymer, the solvent, the graphite material, and the sacrificial metal particles, the silane mixture, and the curing agent to the associated substrate in a single spray, wherein an external effector hydrolyzes the silane mixture to produce silicic acid, which spontaneously polymerizes to siloxane.

[0047] Clause 13 - The method of clause 11 or clause 12, wherein no insulating layer is used.

[0048] Clause 14 - The method of any one of clauses 11 to 13, wherein the external effector is ambient moisture or photons.

[0049] Clause 15 - The method of any one of clauses 11 to 14, wherein the monomer or polymer is selected from the group consisting of epoxies, acrylates, methacrylates, vinyl ethers, cycloaliphatic epoxides, oxetanes, epoxides, photopolymers, siloxanes, and polyureas.

[0050] Clause 16 - The method of any one of clauses 11 to 15, wherein the graphitic material is selected from the group consisting of single-walled carbon nanotubes, double-walled carbon nanotubes, multi-walled carbon nanotubes, single-walled graphene, bi-layer graphene, or multi-layer graphene.

[0051] Clause 17 - The method of any one of clauses 11 to 16, wherein the material that prevents polymerization within the coating is a water scavenger selected from the group consisting of liquid water scavengers, molecular sieves, silica, metal salts, and metal oxides.

[0052] Clause 18 - The method of any one of clauses 11 to 17, wherein the sacrificial metal particles are selected from the group consisting of any metal having a more positive redox potential than iron.

[0053] Clause 19 - The method of any one of clauses 11 to 18, wherein the sacrificial metal particles are selected from the group consisting of zinc, magnesium, aluminum, and alloys thereof.

[0054] Clause 20 - The coating is not selected from the group consisting of 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone, 2,2-dimethoxy-2-phenylacetophenone, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, triphenylsulfonium triflate, triarylsulfonium hexafluoroantimonate salts, triarylsulfonium hexafluorophosphate salts, bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrole- 19. The method of any one of clauses 11 to 19, further comprising a photoinitiator selected from the group consisting of (1-yl)-phenyl)titanium, 5,7-diiodo-3-butoxy-6-fluorone, 2,4,5,7-tetraiodo-3-hydroxy-6-fluorone, and 2,4,5,7-tetraiodo-3-hydroxy-9-cyano-6-fluorone; the curing agent is selected from the group consisting of amines, thiols, phenols, and carboxylic acid anhydrides; and the coupling agent is selected from the group consisting of aminoalkyldialkoxysilanes, dimethoxysilanes, and aminoalkyltrialkoxysilanes.

[0055] Clause 21 - A method of coating an associated substrate with an anticorrosion coating, the method comprising: applying a first curable liquid layer to the associated substrate, the first curable liquid layer having a thickness of at least about 100 micrometers, the first curable liquid layer comprising at least one polymer or at least one monomer, quasi-one-dimensional or quasi-two-dimensional particles, sacrificial metal particles, and a solvent, wherein a percolation threshold of the quasi-one-dimensional or quasi-two-dimensional particles is not reached in the presence of the solvent, and the percolation threshold of the quasi-one-dimensional or quasi-two-dimensional particles is reached when about 1% to about 20% of the solvent has evaporated; and applying a second curable liquid layer over the first curable liquid layer, the second curable liquid layer having a thickness of at least 100 micrometers, after the percolation threshold of the quasi-one-dimensional or quasi-two-dimensional particles has been reached and the viscosity of the first curable liquid layer has increased by more than 50%.

[0056] Clause 22. The method of clause 21, further comprising simultaneously curing the first curable liquid layer and the second curable liquid layer.

[0057] Clause 23 - The method of clause 21 or clause 22, wherein the at least one monomer is at least two monomers, one of the at least two monomers contains at least two epoxy groups, one of the at least two monomers contains a carboxylic acid anhydride, and one of the at least two monomers contains any combination of amino, thiol, and phenolic hydroxyl.

[0058] Clause 24 - The method of any one of clauses 21 to 23, wherein the coating does not substantially absorb water or carbon dioxide and the polymer is continuous without any interfaces.

[0059] Clause 25 - The method of any one of clauses 21 to 24, wherein the first curable liquid layer contains quasi-one-dimensional particles and quasi-two-dimensional particles.

[0060] Clause 26 - The method of any one of clauses 21 to 25, wherein the quasi-one-dimensional particles have a concentration of about 0.1 weight percent to about 2.0 weight percent and the quasi-two-dimensional particles have a concentration of about 2.0 weight percent to about 20 weight percent.

[0061] Clause 27 - The method of any one of clauses 21 to 26, wherein the at least one polymer, upon curing, forms a polyurethane, a polyurea, or a mixture of the two.

[0062] Clause 28 - The method of any one of clauses 21 to 27, wherein the quasi-one-dimensional particles or quasi-two-dimensional particles are selected from graphite particles, carbon nanotubes, graphene, glass flakes, or mica, and the solvent contains an aliphatic hydrocarbon, including methyl ethyl ketone, t-butyl acetate, xylene, hexane, octane, nonane, or decane, and the method avoids amine blush or bloom.

[0063] Clause 29 - The method of any one of clauses 21 to 28, wherein the coating can be applied in less than 24 hours.

[0064] Clause 30 - The method of any one of clauses 21 to 29, which does not include cleaning or sanding the first hardenable liquid layer.

[0065] Clause 31 - The method of any one of clauses 21 to 30, wherein the quasi-one-dimensional particles or quasi-two-dimensional particles are functionalized.

[0066] Clause 32 - The method of any one of clauses 21 to 31, wherein the solvent has a boiling point below 200°C.

[0067] Clause 33 - The method according to any one of clauses 21 to 32, wherein no ketone is used.

[0068] Clause 34 - The method of any one of clauses 21 to 33, wherein the quasi-one-dimensional particles or quasi-two-dimensional particles are graphite material, which is exfoliated, cleaved during dispersion, and chemically bonded to the at least one polymer or at least one monomer.

[0069] Clause 35 - The method of any one of clauses 21 to 33, wherein the quasi-one-dimensional or quasi-two-dimensional particles are glass flakes, and the glass flakes are silyl coated.

[0070] Clause 36 - The method of any one of clauses 21 to 35, wherein volatile organic compounds are present in the coating at less than 25 weight percent.

[0071] Clause 37 - The method of any one of clauses 21 to 36, wherein the second curable liquid layer comprises at least one polymer or at least one monomer, sacrificial metal particles, and a solvent.

[0072] Clause 38 - A corrosion-protective coated substrate, comprising: a first curable liquid layer applied to the substrate, the first curable liquid layer having a thickness of at least about 100 micrometers, the first curable liquid layer comprising at least one polymer or at least one monomer, quasi-one-dimensional particles or quasi-two-dimensional particles, sacrificial metal particles, and a solvent; and a second curable liquid layer having a thickness of at least 100 micrometers on the first curable liquid layer, wherein a percolation threshold of the quasi-one-dimensional particles or quasi-two-dimensional particles is reached and the first curable liquid layer and the second curable liquid are cured simultaneously.

[0073] Clause 39 - The substrate of clause 38, wherein the at least one monomer is at least two monomers, one of the at least two monomers contains at least two epoxy groups, one of the at least two monomers contains a carboxylic acid anhydride, and one of the at least two monomers contains any combination of amino, thiol, and phenolic hydroxyl.

[0074] Clause 40 - The substrate of clause 38 or clause 39, wherein the at least one polymer, when cured, forms a polyurethane, a polyurea, or a mixture of the two, the quasi-one-dimensional particles or the quasi-two-dimensional particles are selected from graphite particles, carbon nanotubes, graphene, glass flakes, or mica, and the solvent contains an aliphatic hydrocarbon, including methyl ethyl ketone, t-butyl acetate, xylene, hexane, octane, nonane, or decane.

[0075] Various embodiments have been described above. It will be apparent to those skilled in the art that the above methods and apparatus may incorporate changes and modifications without departing from the general scope of the present teachings. The present teachings are intended to include all such modifications and modifications insofar as they come within the scope of the appended claims or their equivalents. While the above description contains many specific details, this should not be construed as limiting the scope of the present teachings, but merely as providing examples of some of the aspects of the present teachings. Various other embodiments and modifications are possible within that scope.

[0076] Further, notwithstanding that the numerical ranges and parameters setting forth the broad scope of the present teachings are approximations, the numerical values ​​set forth in the specific examples are reported as precisely as possible, however, any numerical values ​​inherently contain certain errors necessarily resulting from the standard deviation found in their respective testing measurements.

Claims

1. 1. A self-layering corrosion-protective coating comprising: sacrificial metal particles; A graphite material; at least two different monomers or polymers; a silane selected from the group consisting of alkoxysilanes, dialkoxysilanes, trialkoxysilanes, and tetraalkoxysilanes; a material that prevents polymerization of at least one monomer within the coating; A hardener; Including, the monomer or polymer includes at least an epoxy; A coating, wherein the material that prevents polymerization of at least one monomer within the coating is a water scavenger selected from the group consisting of liquid water scavengers, molecular sieves, silica, metal salts, and metal oxides.

2. Binder further comprising 10. The coating of claim 1, wherein the binder is selected from the group consisting of silanes having at least two alkoxy groups.

3. 3. The coating of any one of claims 1 to 2, wherein the monomer or polymer comprises one selected from the group consisting of vinyl ethers and siloxanes.

4. 4. The coating of claim 1, wherein the graphite material is selected from the group consisting of single-walled carbon nanotubes, double-walled carbon nanotubes, multi-walled carbon nanotubes, single-walled graphene, bi-walled graphene, or multi-walled graphene.

5. 5. The coating of any one of claims 1 to 4, wherein the sacrificial metal particles are selected from the group consisting of any metal having a more positive redox potential than iron.

6. 6. The coating of any one of claims 1 to 5, wherein the sacrificial metal particles are selected from the group consisting of zinc, magnesium, aluminum, and alloys thereof.

7. 7. The coating of any one of claims 1 to 6, wherein the curing agent is selected from the group consisting of amines, thiols, phenols, and carboxylic acid anhydrides.

8. The coating may be selected from the group consisting of 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone, 2,2-dimethoxy-2-phenylacetophenone, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, triphenylsulfonium triflate, triarylsulfonium hexafluoroantimonate salts, triarylsulfonium hexafluorophosphate 8. The coating of any one of claims 3 through 7, further comprising a photoinitiator selected from the group consisting of iodo-3-butoxy-6-fluoro-5,5-dimethyl-2,4-diiodo-3-hydroxy-6-fluoro-1,4-dimethyl-2,4-dioxo-1,4-diiodo-3-hydroxy-9-cyano ...

9. 1. A method for a self-layering anticorrosive coating on an associated substrate, comprising: mixing together a monomer or polymer, a solvent, a graphite material, and sacrificial metal particles; adding a material that prevents polymerization within the coating prior to and immediately after application onto the associated substrate; adding a silane mixture; adding a curing agent; curing the coating; Including, the monomer or polymer comprises an epoxy; The method, wherein the material that prevents polymerization within the coating is a water scavenger selected from the group consisting of liquid water scavengers, molecular sieves, silica, metal salts, and metal oxides.

10. applying the mixture of the monomer or polymer, the solvent, the graphite material, and the sacrificial metal particles, the silane mixture, and the curing agent to the associated substrate in a single spray. wherein an external effector hydrolyzes the silane mixture to produce silicic acid, which spontaneously polymerizes to siloxane; The method of claim 9 , wherein the external effector is ambient moisture or photons.

11. 11. The method of claim 9 or claim 10, wherein no insulating layer is used.

12. 12. The method of any one of claims 9 to 11, wherein the monomer or polymer comprises one selected from the group consisting of vinyl ethers and siloxanes.

13. 13. The method of any one of claims 9 to 12, wherein the graphitic material is selected from the group consisting of single-walled carbon nanotubes, double-walled carbon nanotubes, multi-walled carbon nanotubes, single-walled graphene, bi-walled graphene, or multi-walled graphene.

14. 14. The method of any one of claims 9 to 13, wherein the sacrificial metal particles are selected from the group consisting of any metal that has a more positive redox potential than iron.

15. 15. The method of any one of claims 9 to 14, wherein the sacrificial metal particles are selected from the group consisting of zinc, magnesium, aluminum, and alloys thereof.

16. The coating may be selected from the group consisting of 1-hydroxy-cyclohexyl-phenyl-ketone, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone, 2,2-dimethoxy-2-phenylacetophenone, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, triphenylsulfonium triflate, triarylsulfonium hexafluoroantimonate salts, triarylsulfonium hexafluorophosphate salts, bis(η5-2,4-cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrole), 16. The method of any one of claims 9 through 15, further comprising a photoinitiator selected from the group consisting of (2,4,5,7-tetraiodo-3-hydroxy-6-fluorone, 2,4,5,7-tetraiodo-3-hydroxy-9-cyano-6-fluorone, 5,7-diiodo-3-butoxy-6-fluorone, 2,4,5,7-tetraiodo-3-hydroxy-9-cyano-6-fluorone, and a coupling agent selected from the group consisting of aminoalkyldialkoxysilanes, dimethoxysilanes, and aminoalkyltrialkoxysilanes, wherein the curing agent is selected from the group consisting of amines, thiols, phenols, and carboxylic acid anhydrides.

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