High-performance fibers coated with catechol-containing materials

Abstract

The present disclosure relates to high performance fibers (HPF), fiber-reinforced composites, plastics, and other materials. The present disclosure also relates to HPF fibers coated with materials containing catechol polymers, more specifically polycatecholstyrene (PCS). The present disclosure also relates to a process for functionalizing HPF fiber surfaces using PCS-type coatings. In some embodiments, the fibers are polymeric materials such as aramid, liquid crystal polymer (LCP), and ultra-high molecular weight polyethylene (UHMWPE). In one embodiment, the HPF is carbon fiber.

Description

[Technical Field]

[0001] (CROSS-REFERENCE TO RELATED APPLICATIONS) This application claims priority to U.S. Provisional Application No. 63 / 403,237, filed September 1, 2022, which is incorporated herein by reference in its entirety.

[0002] FIELD OF THE INVENTION This disclosure relates to high-performance fiber (HPF), fiber-reinforced composites, plastics, and other materials. This disclosure also relates to HPF fibers coated with materials containing catechol polymers, more specifically polycatechol styrene (PCS). This disclosure also relates to a process for functionalizing HPF fiber surfaces using PCS-type coatings. In some embodiments, the fibers are polymeric materials such as aramid, liquid-crystalline polymer (LCP), and ultra-high molecular-weight polyethylene (UHMWPE). In one embodiment, the HPF is carbon fiber. [Background technology]

[0003] High-performance fibers (HPFs), such as high-performance polymeric fibers (HPP fibers), are very important reinforcing fibers for thermosets, thermoplastics, and other composites. HPP fiber-reinforced plastics (FRPs) can be excellent materials for many applications across a range of industries due to their high specific modulus, specific strength, and corrosion resistance, as well as the inert polymer structure on the surface of HPP fibers. However, the interfacial adhesion between the fiber and the matrix can be weak, and many HPP-FRPs tend to fail at the fiber-matrix interface. This phenomenon can significantly affect the overall mechanical properties of the composite, such as flexural performance and interlaminar shear strength (ILSS). Good interfacial adhesion can effectively transfer stress from the matrix to the reinforcement, which promotes stress dispersion and increases the mechanical strength of the composite.

[0004] Similarly, HPPs, such as carbon fiber (CF), are very important reinforcing fibers for thermosets, thermoplastics, and other composites (CFRPs). CFRPs are excellent materials for many applications across a range of industries due to their high specific modulus, specific strength, and corrosion resistance. However, due to the inert graphite structure on the surface of CFRPs, the interfacial adhesion between the fiber and the matrix tends to be weak, and most CFRPs also tend to fail at the fiber-matrix interface. This phenomenon can significantly affect the overall mechanical properties of the composite, such as flexural performance and interlaminar shear strength (ILSS). Similar to HPPs, good interfacial adhesion in CFRPs can effectively transfer stress from the matrix to the reinforcement, which promotes stress dispersion and increases the mechanical strength of the composite.

[0005] In recent years, many methods have been proposed to improve the interfacial adhesion of fibrous materials to composite matrices, including chemical grafting, sizing, carbon black, electrophoretic deposition, and the introduction of nanoparticles. However, many of these processes are highly toxic, consume large amounts of energy, and are conducted under harsh conditions that may damage the fibers themselves. This has limited the development of these processes for industrial applications. It would be extremely useful to develop an effective, safe, and environmentally friendly process for improving the interfacial properties of HPFs, such as HPP fibers for the development of high-performance HPP-FRPs and CF fibers for the development of high-performance CFRPs.

[0006] One way to improve the interfacial shear strength of fibers relative to a matrix material is by altering the surface "roughness" and thus the surface energy of the fibers. For example, in the case of carbon fibers, this is by depositing or coating carbonaceous materials such as carbon nanotubes, carbon nanofibers, graphene, and carbon black. This method does not chemically functionalize the surface of the CFs, but rather alters the surface "roughness" and thus the surface energy of the fibers. These carbonaceous materials are deposited by several methods that can be expensive, hazardous, or both. These methods include chemical vapor deposition, spray coating, and dip coating. Summary of the Invention

[0007] On the other hand, the present disclosure provides a polycatecholstyrene-based coating on HPP fibers and HPF, such as CF, that is an effective adhesion promoter, which can then be incorporated into various composite materials. Such a coating would also be effective not only on a smaller scale in a laboratory environment, but also in larger scale industrial and commercial applications.

[0008] In one embodiment, the present disclosure relates to a coated high performance fiber (HPF), the HPF being coated with a catechol-containing material, the catechol-containing material comprising a polymer containing catechol, semiquinone, or quinone.

[0009] In another embodiment, the present disclosure relates to a coated HPF as described above, wherein the catechol-containing material coated on the HPF comprises a monomeric, oligomeric, or polymeric catechol or catechol-containing material, wherein the catechol exists as a catechol and / or as a semiquinone and / or as a quinone without the presence of an amine, and wherein the polymer layer optionally comprises at least one of: a) a reactive species separate from the catechol or catechol-containing material, and b) a catalyst, co-catalyst, or accelerator.

[0010] In yet another embodiment, the present disclosure relates to the coated HPF described above, wherein the polymeric material comprises a reactive species separate from the catechol-containing polymer or oligomer, and the reactive species is a urethane component, an epoxy resin, an acrylate monomer or oligomer, a methacrylate monomer or oligomer, a silane, or a combination thereof.

[0011] In one embodiment, the present disclosure provides a method for treating a compound comprising: (i) a urethane component; (ii) a urethane component which is a polyol or an organic compound containing multiple hydroxyl groups, the urethane being linear or branched; (iii) a urethane component which is 1,6-hexanediol, glycerol, Stepanpol PDC-279®, or polycaprolactone triol; (iv) epoxy resins, (v) an epoxy resin which is an epoxy monomer, an epoxy oligomer, a polyepoxide, or a combination thereof, wherein the epoxy is linear or branched; (vi) an epoxy resin that is bisphenol A diglycidyl ether, bisphenol A epoxy resin, bis(4-glycidyloxyphenyl)methane, bisphenol E diglycidyl ether (DGEBE), 2,2'-[1,1-ethanediylbis(4,1-phenyleneoxymethylene)]dioxirane, bisphenol F diglycidyl ether (DGEBF), poly(bisphenol A-co-epichlorohydrin), or a combination thereof; (vii) an acrylate monomer or oligomer; (viii) an acrylate monomer or oligomer comprising a vinyl group and at least one of a carboxylic acid ester and a carboxylic acid nitrile, wherein the acrylate is linear or branched; or (ix) The coated HPF as described above, wherein the acrylate monomer or oligomer is ethyl acrylate, ethylene-methyl acrylate, methyl methacrylate, 2-chloroethyl vinyl ether, 2-hydroxyethyl acrylate, hydroxyethyl methacrylate, butyl acrylate, trimethylolpropane triacrylate (TMPTA), or a combination thereof.

[0012] In another embodiment, the present disclosure relates to the above coated HPF, wherein the polymer layer comprises a catalyst, co-catalyst, or accelerator, and the catalyst, co-catalyst, or accelerator is a urethane catalyst that promotes a urethane polymerization reaction, an epoxy catalyst that promotes an epoxy polymerization reaction, an acrylate catalyst that promotes an acrylate polymerization reaction, or a combination thereof.

[0013] In yet another embodiment, the present disclosure provides a process for preparing a catalyst, co-catalyst, or promoter comprising: (i) a urethane catalyst that promotes the urethane polymerization reaction; (ii) a urethane catalyst that promotes the urethane polymerization reaction, which is 1,4-diazabicyclo[2.2.2]octane, K-KAT 6212, benzyldimethylamine, or a combination thereof; (iii) an epoxy catalyst that promotes epoxy polymerization; (iv) an epoxy catalyst which is 1,4-diazabicyclo[2.2.2]octane; (v) an acrylate catalyst that promotes acrylate polymerization; or (vi) The coated HPF is an acrylate catalyst that is an acrylic polymerization accelerator or a free radical polymerization accelerator.

[0014] In one embodiment, the present disclosure provides a coating of polymeric material comprising: (i) about 5 nanometers to about 100 microns; (ii) about 15 nanometers to about 50 microns; (iii) about 15 nanometers to about 15 microns; (iv) from about 50 nanometers to less than about 15 microns; or (v) The coated HPF described above has a thickness of about 50 nanometers to about 1.5 microns.

[0015] In another embodiment, the present disclosure relates to the above coated HPF, wherein the catechol-containing polymer or oligomer comprises polycatecholstyrene (PCS).

[0016] In yet another embodiment, the present disclosure relates to the above coated HPF, wherein the molecular weight is in the range of 100 to 1,000,000.

[0017] In one embodiment, the present disclosure relates to the above coated HPF, wherein the PCS comprises about 15% catechol to about 85% catechol.

[0018] In another embodiment, the present disclosure relates to the above coated HPF, wherein the PCS comprises about 25% catechol or about 35% catechol.

[0019] In yet another embodiment, the present disclosure relates to the above coated HPF, wherein the HPF is a polymer.

[0020] In one embodiment, the present disclosure relates to the coated HPF described above, wherein the HPF is an aramid, super aramid, aramid copolymer, meta aramid, LCP, UHMWPE polymer, polyamide, polyester, polyolefin, or a combination thereof.

[0021] In another embodiment, the present disclosure relates to the above coated HPF, wherein the HPF is a carbon fiber.

[0022] In yet another embodiment, the present disclosure relates to a fiber-reinforced composite comprising one or more HPFs described above.

[0023] In one embodiment, the present disclosure provides a polymer comprising a matrix polymer comprising: The fiber-reinforced composite is selected from polypropylene, polyethylene, polycarbonate, polyvinyl chloride, polyether ether ketone, polyethersulfone, polyphenylene sulfide, polyamide, polymethyl methacrylate, polyetherimide, acetal, sulfone polymer, ethylene-vinyl acetate, liquid crystal polymer, polybutylene terephthalate, acrylonitrile butadiene styrene, fluoropolymer, thermoplastic elastomer, thermoplastic polyurethane, polycyclohexylene dimethylene terephthalate, epoxy resin, polyester resin, vinyl ester resin, phenolic resin, polyimide, polyurethane, polystyrene, silicone resin, cyanate ester, melamine-formaldehyde resin, polydicyclopentadiene, polyarylate, polybenzimidazole, polychlorotrifluoroethylene, methyl methacrylate-butadiene-styrene, polyacrylonitrile, polyhydroxyalkanoate, polylactic acid, polyhydroxybutalate, and polyoxymethylene copolymer.

[0024] In another embodiment, the present disclosure relates to a method for preparing the above-described HPF, the method comprising exposing the HPF to a pre-polymerized catechol-containing polymer dissolved in one or more solvents.

[0025] In yet another embodiment, the present disclosure relates to a method for surface functionalization of the above-described HPF surface, comprising exposing the HPF to a pre-polymerized catechol-containing polymer dissolved in one or more solvents.

[0026] In one embodiment, the present disclosure relates to a coated HPF as described above, wherein the HPF is completely or partially coated with a material comprising a PCS polymer.

[0027] In another embodiment, the present disclosure relates to an article of manufacture comprising the fiber-reinforced composite described above.

[0028] In yet another embodiment, the present disclosure provides a method for applying a coating to at least one surface of a substrate made from the fiber reinforced composite material described above, the method comprising: applying a graphene or zinc particle-filled PCS layer as a primer to at least one surface of a substrate; and applying a coating to the zinc or graphene particle filled PCS layer.

[0029] In one embodiment, the present disclosure provides: the zinc or graphene particle-filled adhesive PCS layer has a thickness of 200 nm to 100 μm; and / or The method as described above, wherein the PCS layer is filled with graphene particles and comprises 0.5 wt% to 2 wt% graphene.

[0030] In another embodiment, the present disclosure relates to a substrate comprising, on at least one surface thereof, a coating applied by practicing the above-described method.

[0031] In yet another embodiment, the present disclosure relates to an aircraft component comprising the substrate described above. [Brief explanation of the drawings]

[0032] [Figure 1] 1 depicts a high performance fiber (HPF) coated with at least one layer of a catechol-containing material, and other optional layers including one or more catechol-containing layers. [Figure 2A] SEM micrographs of uncoated aramid fiber (2A, 2D, 2G), aramid fiber treated with a 6% ZnCl bath (2B, 2E, 2H), and aramid fiber treated with a ZnCl bath and PCS coating (2C, 2F, 2I) are shown. [Figure 2B] SEM micrographs of uncoated aramid fiber (2A, 2D, 2G), aramid fiber treated with a 6% ZnCl bath (2B, 2E, 2H), and aramid fiber treated with a ZnCl bath and PCS coating (2C, 2F, 2I) are shown. [Figure 2C] SEM micrographs of uncoated aramid fiber (2A, 2D, 2G), aramid fiber treated with a 6% ZnCl bath (2B, 2E, 2H), and aramid fiber treated with a ZnCl bath and PCS coating (2C, 2F, 2I) are shown. [Figure 2D] SEM micrographs of uncoated aramid fiber (2A, 2D, 2G), aramid fiber treated with a 6% ZnCl bath (2B, 2E, 2H), and aramid fiber treated with a ZnCl bath and PCS coating (2C, 2F, 2I) are shown. [Figure 2E] SEM micrographs of uncoated aramid fiber (2A, 2D, 2G), aramid fiber treated with a 6% ZnCl bath (2B, 2E, 2H), and aramid fiber treated with a ZnCl bath and PCS coating (2C, 2F, 2I) are shown. [Figure 2F]SEM micrographs of uncoated aramid fiber (2A, 2D, 2G), aramid fiber treated with a 6% ZnCl bath (2B, 2E, 2H), and aramid fiber treated with a ZnCl bath and PCS coating (2C, 2F, 2I) are shown. [Figure 2G] SEM micrographs of uncoated aramid fiber (2A, 2D, 2G), aramid fiber treated with a 6% ZnCl bath (2B, 2E, 2H), and aramid fiber treated with a ZnCl bath and PCS coating (2C, 2F, 2I) are shown. [Figure 2H] SEM micrographs of uncoated aramid fiber (2A, 2D, 2G), aramid fiber treated with a 6% ZnCl bath (2B, 2E, 2H), and aramid fiber treated with a ZnCl bath and PCS coating (2C, 2F, 2I) are shown. [Figure 2I] SEM micrographs of uncoated aramid fiber (2A, 2D, 2G), aramid fiber treated with a 6% ZnCl bath (2B, 2E, 2H), and aramid fiber treated with a ZnCl bath and PCS coating (2C, 2F, 2I) are shown. [Figure 3A] 3A, 3B, and 3C depict SEM images of polycatecholstyrene (PCS)-coated carbon fibers (CF), corresponding to magnifications of 7Kx, 2x, and 700x, respectively. [Figure 3B] 3A, 3B, and 3C depict SEM images of polycatecholstyrene (PCS)-coated carbon fibers (CF), corresponding to magnifications of 7Kx, 2x, and 700x, respectively. [Figure 3C] 3A, 3B, and 3C depict SEM images of polycatecholstyrene (PCS)-coated carbon fibers (CF), corresponding to magnifications of 7Kx, 2x, and 700x, respectively. [Figure 4A]4A, 4C, 4E, and 4B show SEM micrographs of uncoated (4A, 4C, 4E) and PCS-coated (4B, 4D, 4F) Teijin Tenax chopped carbon fiber and PCS-coated chopped carbon fiber, respectively. [Figure 4B] 4A, 4C, 4E, and 4B show SEM micrographs of uncoated (4A, 4C, 4E) and PCS-coated (4B, 4D, 4F) Teijin Tenax chopped carbon fiber and PCS-coated chopped carbon fiber, respectively. [Figure 4C] 4A, 4C, 4E, and 4B show SEM micrographs of uncoated (4A, 4C, 4E) and PCS-coated (4B, 4D, 4F) Teijin Tenax chopped carbon fiber and PCS-coated chopped carbon fiber, respectively. [Figure 4D] 4A, 4C, 4E, and 4B show SEM micrographs of uncoated (4A, 4C, 4E) and PCS-coated (4B, 4D, 4F) Teijin Tenax chopped carbon fiber and PCS-coated chopped carbon fiber, respectively. [Figure 4E] 4A, 4C, 4E, and 4B show SEM micrographs of uncoated (4A, 4C, 4E) and PCS-coated (4B, 4D, 4F) Teijin Tenax chopped carbon fiber and PCS-coated chopped carbon fiber, respectively. [Figure 4F] 4A, 4C, 4E, and 4B show SEM micrographs of uncoated (4A, 4C, 4E) and PCS-coated (4B, 4D, 4F) Teijin Tenax chopped carbon fiber and PCS-coated chopped carbon fiber, respectively. [Figure 5A]Figure 5 depicts SEM micrographs of recycled carbon fibers coated with PCS. (5A, 5C) are recycled carbon fibers that have been washed with acetone, and (5B, 5D) are recycled carbon fibers that have been treated with a poly(catecholstyrene) (PCS) coating. [Figure 5B] Figure 5 depicts SEM micrographs of recycled carbon fibers coated with PCS. (5A, 5C) are recycled carbon fibers that have been washed with acetone, and (5B, 5D) are recycled carbon fibers that have been treated with a poly(catecholstyrene) (PCS) coating. [Figure 5C] Figure 5 depicts SEM micrographs of recycled carbon fibers coated with PCS. (5A, 5C) are recycled carbon fibers that have been washed with acetone, and (5B, 5D) are recycled carbon fibers that have been treated with a poly(catecholstyrene) (PCS) coating. [Figure 5D] Figure 5 depicts SEM micrographs of recycled carbon fibers coated with PCS. (5A, 5C) are recycled carbon fibers that have been washed with acetone, and (5B, 5D) are recycled carbon fibers that have been treated with a poly(catecholstyrene) (PCS) coating. [Figure 6A] 6A and 6B depict SEM micrographs of recycled carbon fibers coated with poly(catecholstyrene) (PCS). Figures 6A and 6C relate to fibers coated with a 0.5% PCS solution, and Figures 5B and 5D relate to a 3% PCS solution used to coat the carbon fibers, which heavily coats the fibers in a thick PCS coating. [Figure 6B] 6A and 6B depict SEM micrographs of recycled carbon fibers coated with poly(catecholstyrene) (PCS). Figures 6A and 6C relate to fibers coated with a 0.5% PCS solution, and Figures 5B and 5D relate to a 3% PCS solution used to coat the carbon fibers, which heavily coats the fibers in a thick PCS coating. [Figure 6C]6A and 6B depict SEM micrographs of recycled carbon fibers coated with poly(catecholstyrene) (PCS). Figures 6A and 6C relate to fibers coated with a 0.5% PCS solution, and Figures 5B and 5D relate to a 3% PCS solution used to coat the carbon fibers, which heavily coats the fibers in a thick PCS coating. [Figure 6D] 6A and 6B depict SEM micrographs of recycled carbon fibers coated with poly(catecholstyrene) (PCS). Figures 6A and 6C relate to fibers coated with a 0.5% PCS solution, and Figures 5B and 5D relate to a 3% PCS solution used to coat the carbon fibers, which heavily coats the fibers in a thick PCS coating. [Figure 7A] This is a process for dip-coating carbon fibers with PCS sizing solution. Carbon fibers (Figure 7A) were dipped into the solution (Figures 7B and 7C). The air-dried sample is shown in (Figure 7D). [Figure 7B] This is a process for dip-coating carbon fibers with PCS sizing solution. Carbon fibers (Figure 7A) were dipped into the solution (Figures 7B and 7C). The air-dried sample is shown in (Figure 7D). [Figure 7C] This is a process for dip-coating carbon fibers with PCS sizing solution. Carbon fibers (Figure 7A) were dipped into the solution (Figures 7B and 7C). The air-dried sample is shown in (Figure 7D). [Figure 7D] This is a process for dip-coating carbon fibers with PCS sizing solution. Carbon fibers (Figure 7A) were dipped into the solution (Figures 7B and 7C). The air-dried sample is shown in (Figure 7D). [Figure 7E] Figure 7 shows two layers of as-received Chomarat® carbon fiber (0 / 90) at three different magnifications. Figure 7H shows the carbon fiber before burn-off, and Figures 7I and 7J are the carbon fiber after burn-off. Figures 7K, 7L, and 7M are SEM micrographs of the carbon fiber after furnace burn-off. [Figure 7F]Figure 7 shows two layers of as-received Chomarat® carbon fiber (0 / 90) at three different magnifications. Figure 7H shows the carbon fiber before burn-off, and Figures 7I and 7J are the carbon fiber after burn-off. Figures 7K, 7L, and 7M are SEM micrographs of the carbon fiber after furnace burn-off. [Figure 7G] Figure 7 shows two layers of as-received Chomarat® carbon fiber (0 / 90) at three different magnifications. Figure 7H shows the carbon fiber before burn-off, and Figures 7I and 7J are the carbon fiber after burn-off. Figures 7K, 7L, and 7M are SEM micrographs of the carbon fiber after furnace burn-off. [Figure 7H] Figure 7 shows two layers of as-received Chomarat® carbon fiber (0 / 90) at three different magnifications. Figure 7H shows the carbon fiber before burn-off, and Figures 7I and 7J are the carbon fiber after burn-off. Figures 7K, 7L, and 7M are SEM micrographs of the carbon fiber after furnace burn-off. [Figure 7I] Figure 7 shows two layers of as-received Chomarat® carbon fiber (0 / 90) at three different magnifications. Figure 7H shows the carbon fiber before burn-off, and Figures 7I and 7J are the carbon fiber after burn-off. Figures 7K, 7L, and 7M are SEM micrographs of the carbon fiber after furnace burn-off. [Figure 7J] Figure 7 shows two layers of as-received Chomarat® carbon fiber (0 / 90) at three different magnifications. Figure 7H shows the carbon fiber before burn-off, and Figures 7I and 7J are the carbon fiber after burn-off. Figures 7K, 7L, and 7M are SEM micrographs of the carbon fiber after furnace burn-off. [Figure 7K] Figure 7 shows two layers of as-received Chomarat® carbon fiber (0 / 90) at three different magnifications. Figure 7H shows the carbon fiber before burn-off, and Figures 7I and 7J are the carbon fiber after burn-off. Figures 7K, 7L, and 7M are SEM micrographs of the carbon fiber after furnace burn-off. [Figure 7L]Figure 7 shows two layers of as-received Chomarat® carbon fiber (0 / 90) at three different magnifications. Figure 7H shows the carbon fiber before burn-off, and Figures 7I and 7J are the carbon fiber after burn-off. Figures 7K, 7L, and 7M are SEM micrographs of the carbon fiber after furnace burn-off. [Figure 7M] Figure 7 shows two layers of as-received Chomarat® carbon fiber (0 / 90) at three different magnifications. Figure 7H shows the carbon fiber before burn-off, and Figures 7I and 7J are the carbon fiber after burn-off. Figures 7K, 7L, and 7M are SEM micrographs of the carbon fiber after furnace burn-off. [Figure 7-1] FTIR transmittance as a function of wavenumber for PCS polymer 240K molecular weight, the same polymer at 1% concentration in acetone used for 5 minute dip coating, 15 minute dip coating, and 30 minute dip coating. [Figure 8] FTIR scans of as-received and burned-off carbon fibers are shown. [Figure 9A] SEM of as-received carbon fiber coated with a 0.5% PCS polymer solution in acetone that was dip coated for 30 minutes. The PCS used is a 240K Dalton molecular weight material. [Figure 9B] SEM of as-received carbon fiber coated with a 0.5% PCS polymer solution in acetone that was dip coated for 30 minutes. The PCS used is a 240K Dalton molecular weight material. [Figure 9C] SEM of as-received carbon fiber coated with a 0.5% PCS polymer solution in acetone that was dip coated for 30 minutes. The PCS used is a 240K Dalton molecular weight material. [Figure 10A] SEM of as-received carbon fiber coated with a 1.0% PCS polymer solution in acetone that was dip coated for 30 minutes. The PCS used is a 240K Dalton molecular weight material. [Figure 10B] SEM of as-received carbon fiber coated with a 1.0% PCS polymer solution in acetone that was dip coated for 30 minutes. The PCS used is a 240K Dalton molecular weight material. [Figure 10C] SEM of as-received carbon fiber coated with a 1.0% PCS polymer solution in acetone that was dip coated for 30 minutes. The PCS used is a 240K Dalton molecular weight material. [Figure 11] Figure 1 shows FTIR scans of as-received carbon fibers coated with 1% PCS in acetone solvent by dip coating for 5, 15, and 30 minutes. The PCS used is a 240K Dalton molecular weight material. [Figure 12A] SEM of as-received carbon fibers coated with a 1.5% PCS polymer solution in acetone that has been dip coated for 5 minutes. [Figure 12B] SEM of as-received carbon fibers coated with a 1.5% PCS polymer solution in acetone that has been dip coated for 5 minutes. [Figure 12C] SEM of as-received carbon fibers coated with a 1.5% PCS polymer solution in acetone that has been dip coated for 5 minutes. [Figure 13A] SEM of as-received carbon fibers coated with a 1.5% PCS polymer solution in acetone that has been dip coated for 15 minutes. [Figure 13B] SEM of as-received carbon fibers coated with a 1.5% PCS polymer solution in acetone that has been dip coated for 15 minutes. [Figure 13C] SEM of as-received carbon fibers coated with a 1.5% PCS polymer solution in acetone that has been dip coated for 15 minutes. [Figure 14A]SEM of as-received carbon fibers coated with a 1.5% PCS polymer solution in acetone that has been dip coated for 30 minutes. [Figure 14B] FIG. 10 is an SEM of as-received carbon fibers coated with a 1.5% PCS polymer solution in acetone that has been dip coated for 30 minutes. [Figure 14C] FIG. 10 is an SEM of as-received carbon fibers coated with a 1.5% PCS polymer solution in acetone that has been dip coated for 30 minutes. [Figure 15] Figure 1 shows FTIR scans of as-received carbon fibers coated with 1.5% PCS in acetone solvent by dip coating for 5, 15, and 30 minutes. The PCS used is a 240K Dalton molecular weight material. [Figure 16A] SEM of as-received carbon fibers coated with a 2.0% PCS polymer solution in acetone that has been dip coated for 5 minutes. [Figure 16B] SEM of as-received carbon fibers coated with a 2.0% PCS polymer solution in acetone that has been dip coated for 5 minutes. [Figure 16C] SEM of as-received carbon fibers coated with a 2.0% PCS polymer solution in acetone that has been dip coated for 5 minutes. [Figure 17A] FIG. 10 is an SEM of as-received carbon fibers coated with a 2.0% PCS polymer solution in acetone that has been dip coated for 15 minutes. [Figure 17B] FIG. 10 is an SEM of as-received carbon fibers coated with a 2.0% PCS polymer solution in acetone that has been dip coated for 15 minutes. [Figure 17C] FIG. 10 is an SEM of as-received carbon fibers coated with a 2.0% PCS polymer solution in acetone that has been dip coated for 15 minutes. [Figure 18A]FIG. 10 is an SEM of as-received carbon fibers coated with a 2.0% PCS polymer solution in acetone that has been dip coated for 30 minutes. [Figure 18B] FIG. 10 is an SEM of as-received carbon fibers coated with a 2.0% PCS polymer solution in acetone that has been dip coated for 30 minutes. [Figure 18C] FIG. 10 is an SEM of as-received carbon fibers coated with a 2.0% PCS polymer solution in acetone that has been dip coated for 30 minutes. [Figure 19] Figure 1 shows FTIR scans of as-received carbon fibers coated with 2.0% PCS in acetone solvent by dip coating for 5, 15, and 30 minutes. The PCS used is a 240K Dalton molecular weight material. [Figure 20A] 1 shows the top surface of the carbon fiber after dip coating at 5, 15, and 30 minutes. [Figure 20B] The bottom surface of the carbon fiber is shown after dip coating at 5, 15, and 30 minutes. [Figure 21] 1 shows carbon fibers that have been sized with PCS via dip coating and then used to make a laminate with a PEEK matrix. DETAILED DESCRIPTION OF THE INVENTION

[0033] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure.

[0034] The following terms are used to describe this disclosure. If a term is not specifically defined herein, the term will be given its art-recognized meaning by one of ordinary skill in the art applying the term in context to its use in describing this disclosure.

[0035] In this disclosure, the singular forms "a," "an," and "the" include plural referents, and reference to a particular numerical value includes at least that particular value unless the context clearly dictates otherwise. Thus, for example, reference to a "material" is a reference to at least one such material and equivalents thereof known to those skilled in the art, and so forth.

[0036] When a value is expressed as an approximation, by use of the descriptors "about" or "substantially," it will be understood that the particular value forms another embodiment. In general, use of the terms "about" or "substantially" refers to approximations that may vary depending on the desired properties sought to be achieved by the disclosed subject matter and should be interpreted based on their function in the specific context in which it is used. One of ordinary skill in the art will be able to interpret this as routine. In some cases, the number of significant digits used in a particular value may be one non-limiting way of determining the extent of the term "about" or "substantially." In other cases, the gradations used in a series of values ​​may determine the intended range available for the term "about" or "substantially" for each value. Where present, all ranges are inclusive and combinable; that is, reference to values ​​stated in ranges includes all values ​​within that range.

[0037] When lists are presented, it is to be understood that each individual element of that list and every combination of that list is to be construed as a separate embodiment unless otherwise stated. For example, a list of embodiments presented as "A, B, or C" should be construed as including the embodiments "A," "B," "C," "A or B," "A or C," "B or C," or "A, B, or C."

[0038] It is to be understood that certain features of the present disclosure, which are, for clarity, described herein in the context of separate embodiments, may also be provided in combination in a single embodiment. That is, unless clearly contradictory or excluded, each individual embodiment is construed as combinable with any other embodiment, and such combinations are considered to be separate embodiments. Conversely, various features of the present disclosure, which are, for brevity, described in the context of a single embodiment, may also be provided separately or in any subcombination. It is further noted that the claims may be drafted to exclude any optional element. As such, the above passage is intended to serve as a basis prior to the use of exclusive terminology, such as "solely," "only," and the like, or the use of a "negative" limitation, in connection with the recitation of claim elements. Finally, while an embodiment may be described as part of a series of steps or part of a more general structure, each such step may also be considered a separate embodiment in itself.

[0039] The following describes exemplary embodiments of the present disclosure in the context of high performance fibers (HPF). The present disclosure relates to HPF coated with a catechol-containing material. A preferred catechol-containing material includes polycatecholstyrene (PCS), as described below. While various embodiments disclosed below may refer to PCS or PCS-type materials, it should be understood that PCS is used as an example of a catechol-containing material. The term PCS-type is also used to refer to materials that contain catechol and are similar to PCS.

[0040] In one embodiment, the high performance fibers or super fibers used in the coatings of the present disclosure include aromatic polyamides (aramids), such as Kevlar™, gel-spun high modulus polyethylene (UHMWPE), superaramids and aramid copolymers, melt-spun liquid crystalline aromatic polyesters (LCPs), and carbon fibers.

[0041] In another embodiment, other HPP fibers for use in this disclosure include polyamides, polyolefins, and polyesters. These include general-purpose fibers such as melt-spun nylon 6, nylon 6,6, high-performance aromatic polyamides, or acid-spun aramids from monomers, or meta-aramids such as Nomex®, and their copolymers. Examples of polyolefins include general-purpose fibers from melt-spun LLDPE or polypropylene, and high-performance polyethylene and polypropylene fibers that are gel-spun. Examples of polyesters include general-purpose fibers from melt-spun polyesters such as PET, PTT, and PBT, and high-performance aromatic polyesters, including arrester or liquid crystal polymers (LCP), and / or their copolymers.

[0042] I. Aromatic polyamide or aramid Aramid fibers used for coatings in this disclosure include those that are heat-resistant and strong synthetic fibers used in aerospace and military applications, for ballistic-rated body armor fabrics and ballistic composites, in marine rigging, marine hull reinforcement, and as an asbestos replacement. The chain molecules in the fiber are highly oriented along the fiber axis. As a result, a higher percentage of chemical bonds contribute to fiber strength than many other synthetic fibers. Aramids have very high melting points (above 500°C). Common aramid brand names include Kevlar®, Nomex®, and Twaron®. Aramids share a high degree of orientation with other fibers, such as ultra-high molecular weight polyethylene, and this characteristic governs their properties. Further examples of aramids include Technora® and Vectran®.

[0043] Aramids have one or more of the following properties: ·High tensile strength High wear resistance ·lightweight High chemical resistance, good resistance to organic solvents ·Excellent durability ·Thermal stability ·Heat resistance / flame resistance ·Low moisture absorption Cut / slash / impact resistant Non-conductive Very high melting point (over 500°C) Good fabric integrity at high temperatures Sensitivity to acids and salts Sensitivity to ultraviolet radiation - Easily accumulates static charge unless finished Para-aramid fibers such as Kevlar® and Twaron® offer outstanding strength-to-weight properties High cord modulus Low creep Low elongation at break (approximately 3.5%) Difficult to dye - usually solution dyed

[0044] End uses for these fibers include: Protective textiles and clothing / PPE ·Specialty industrial fabrics Ropes / cables ·Aerospace / Military / Law Enforcement Heavy lift slings / straps ·Special electronic equipment ·Flexible composites / expandables Fire-resistant clothing Thermal clothing and helmets ·Body protective equipment ·Composite materials Asbestos replacement (e.g. brake linings) ·Hot air filter cloth Tires, now with Sulfron® (sulfur-modified Twaron®) Mechanical rubber product reinforcement Ropes and cables V-belts (automobiles, machinery, equipment, etc.) Fire dance wick Fiber optic cable system ·Canvas Sports equipment Drum heads Wind instrument reeds Loudspeaker diaphragm Hull material Fiber-reinforced concrete Reinforced thermoplastic pipes Tennis strings Hockey stick Snowboarding Jet engine enclosures Fishing reel drag system. Asphalt reinforcement Prusik for rock climbers.

[0045] [ka]

[0046] In one embodiment, the aramid of the present disclosure for PCS-type coatings has a molecular structure as shown above, with generally hexagonal rings alternately bonded to either two NH groups or two CO groups. The attachment points on each ring are opposite each other, meaning that it is classified as a para-aramid. In aramids, the aromatic rings are connected via amide linkages, each containing a CO group bonded to an NH group. Aramids are divided into two main types depending on where the linkage is attached to the ring. Numbering the carbon atoms around the ring in order, para-aramids have linkages attached to the 1- and 4-positions, while meta-aramids have linkages at the 1- and 3-positions. That is, the attachment points are opposite each other in para-aramids and two atoms apart in meta-aramids. Therefore, the illustrative diagram shows para-aramids.

[0047] The meta-aramid fiber Nomex® used in the PCS-type coating in this disclosure is characterized by its excellent heat resistance, as it does not melt or ignite in normal levels of oxygen. It is widely used in the production of protective clothing, air filtration, thermal and electrical insulation, and asbestos replacements. Meta-aramids include Teijinconex®, Arawin®, New Star®, X-Fiper®, and meta-aramid Kermel® variants.

[0048] Para-aramid fibers used in PCS-type coatings in this disclosure include Kevlar®, Twaron®, Heracron®, and Taparan®. Para-aramids are used for "ballistic" body armor in many high-tech applications, such as aerospace and military applications. Both meta-aramid and para-aramid fibers can be used to make aramid paper. Aramid paper is used as an electrical insulating material and a building material for making honeycomb cores. Aramid papers include meta-aramid and para-aramid papers, such as Nomex® paper and Metastar® paper. Aramid fibers can be made into fibers, chopped fibers, powder, or pulp.

[0049] In addition to meta-aramids such as Nomex®, other variations used in the PCS type coatings of this disclosure fall within the range of aramid fibers, primarily of the copolyamide type, best known under the trade name Technora®.

[0050] II. Liquid Crystal Polymer (LCP) Fiber

[0051] [ka]

[0052] Molecular and crystalline orientation in spun polymers For use in the PCS-type coatings of the present disclosure, in one embodiment, an LCP based on a copolymer of p-hydroxybenzoic acid (HBA) and 2-hydroxy-6-naphthoic acid (HNA) (HBA / HNA) can be used, which has been used to produce Vectran® HT LCP fibers. When a liquid crystal polymer is spun into a fiber, some alignment of the crystalline domains occurs, as shown schematically above. While in amorphous polymers such as PET, some alignment in the spinning direction also occurs, in LCPs, the aligned crystalline domains result in much higher tensile properties, such as strength and modulus.

[0053] The polyester-based LCP fibers used in the PCS-type coatings of this disclosure can reach tenacities in excess of 3.5 GPa (greater than 28 gpd) with elongation at break of less than 4%. Key advantages of LCPs over competing high-performance fibers include dimensional and property stability over a wide range of temperatures, as well as a long service life due to enhanced resistance to repeated abrasion, flex fatigue, and chemical exposure. This class of fibers is increasingly being used in demanding aerospace, military, and industrial applications across a wide range of environments.

[0054] Specific applications of LCP fibers used in the PCS-type coatings of this disclosure include low-creep ropes, multicomponent cables and umbilicals, and industrial textiles. Flexible composites using coated Vectran® textiles are used in many technical end uses, such as rapidly deployable inflatable structures, lighter-than-air vehicles, and air-supporting tension members. LCP fibers are used in similar applications to UHMWPE (ultra-high molecular weight polyethylene) and aramid fibers. For example, rope handlers in harsh marine environments prefer lighter UHMWPE fibers, but LCP fibers are used at high temperatures, which can cause dimensional instability in UHMWPE. In cables and coated textiles, LCP's near-zero moisture content eliminates fiber outgassing during extrusion, which can cause blistering of polymer coatings or jackets. In industrial textiles, LCP's improved bend-fold and abrasion resistance compared to aramid reduces premature fatigue failure in coated textiles and personal protective equipment.

[0055] LCPs are classified by the location of the liquid crystal core. Main chain liquid crystal polymers (MCLCPs) have a liquid crystal core in the main chain. Side chain liquid crystal polymers (SCLCPs) have pendant side chains containing the liquid crystal core. Main chain LCPs have rigid rod-like mesogens in the polymer backbone, which indirectly leads to the high melting temperature of this type of LCP. In side chain LCPs, the mesogens are in the polymer side chains. The mesogens are usually connected to the backbone via a flexible spacer.

[0056] The mesogens in LCPs can self-assemble to form liquid crystal domains under different conditions. Based on the mechanism of aggregation and ordering, LCPs can be broadly divided into two subcategories: lyotropic and thermotropic.

[0057] Lyotropic main-chain LCPs have a rigid mesogenic core (such as an aromatic ring) in the backbone. Lyotropic main-chain LCPs have primarily been used to produce high-strength fibers such as Kevlar. Lyotropic side-chain LCPs, such as alkylpolyoxyethylene surfactants attached to polysiloxane polymers, can be applied in personal care products such as liquid soaps.

[0058] Thermotropic LCPs can be processed if their melting temperature is much lower than their decomposition temperature. Above their melting and glass transition temperatures, but below their clearing point, they form liquid crystals. Other systems exist, such as phototropic systems.

[0059] The present disclosure also relates to a method for coating the HPF with a catechol-containing material.

[0060] III. Carbon Fiber Because carbon fibers are lightweight and have excellent strength and elastic modulus, they are combined with various matrix resins to form composite materials, which are used in a variety of fields, including aircraft components, spacecraft components, automobile components, ship components, building materials, and sporting goods. In order to impart the excellent characteristics of carbon fibers to composite materials containing carbon fibers, excellent adhesion between the carbon fibers and the matrix resin is important.

[0061] To improve the adhesion between carbon fibers and matrix resins, carbon fibers are typically subjected to oxidation, such as gas-phase oxidation and liquid-phase oxidation, which introduces oxygen-containing functional groups onto the surface of the carbon fibers. For example, a disclosed method involves subjecting carbon fibers to electrolysis to improve interlaminar shear strength, which is an indicator of adhesion. However, due to the recent demand for highly characterized composite materials, the adhesion achieved by such oxidation alone is becoming insufficient.

[0062] Carbon fibers are brittle and have poor bonding and abrasion resistance, so they are prone to fuzzing or breakage during advanced processing. To address this problem, methods of coating carbon fibers have been disclosed.

[0063] In one embodiment, the present disclosure relates to individual and multiple carbon fibers coated with a thin poly(catecholstyrene) (PCS) film. This thin polymer film functionalizes the previously inert carbon fiber surface with catechol moieties that can aid in adhesion to various thermoset, thermoplastic, and other composite matrices. The coating method involves stirring raw carbon fibers in an organic solvent containing dissolved PCS. The PCS from the solution forms bonds with the carbon fiber surface, leaving a thin film deposited thereon. Following the coating reaction, the fibers are filtered, rinsed with isopropyl alcohol and DI water, and dried, preferably in a vacuum chamber, to remove any residual solvent.

[0064] This one-step coating process has advantages over many other coating processes. In one embodiment, an advantage of PCS is that it is prepolymerized, so in one embodiment of the coating process, a preformed catechol-containing polymer interacts with the carbon fiber surface.

[0065] The carbon fibers may be chopped strands, and may be any of PAN type, pitch type, and others, and the starting material and production method thereof are not limited. The length of the carbon fiber chopped strands is not critical, but in one embodiment, it is 5 microns to 50 mm. The diameter and number of filaments constituting the carbon fiber chopped strands are also not critical, but in one embodiment, the diameter is typically 500 nm to 50 microns. The number of filaments is typically 100 to 100,000. A sizing agent may be applied to the carbon fiber chopped strands in advance.

[0066] IV. Coating of Catechol-Containing Materials onto High-Performance Fibers The high performance fibers (HPF) described above may be coated with at least one layer comprising a catechol-containing material, such as PCS, as described below.

[0067] In one aspect, the present disclosure is directed to a HPF coated with a catechol-containing material, such as a PCS comprising a catechol-containing polymer or oligomer, where the catechol exists as a catechol and / or as a semiquinone and / or as a quinone without the presence of a primary or secondary amine, and the polymeric material optionally comprises at least one of: a) a reactive species separate from the catechol-containing polymer or oligomer, and b) a catalyst, co-catalyst, or accelerator.

[0068] In some embodiments, the catechol-containing material coated on the HPF comprises a catechol-containing polymer or oligomer, where the catechol exists as a catechol and / or as a semiquinone and / or as a quinone without the presence of a primary or secondary amine.

[0069] In some embodiments, the catechol-containing material coated on the HPF comprises a catechol-containing polymer or oligomer, where the catechol exists as a catechol and / or as a semiquinone and / or as a quinone without the presence of a primary or secondary amine, and also comprises a reactive species separate from the catechol-containing polymer or oligomer.

[0070] In some embodiments, the catechol-containing material coated on the HPF comprises a catechol-containing polymer or oligomer, where the catechol exists as a catechol and / or as a semiquinone and / or as a quinone without the presence of a primary or secondary amine, and also includes a catalyst, co-catalyst, or accelerator.

[0071] In some embodiments, the catechol-containing material coated on the HPF comprises a catechol-containing polymer or oligomer, where the catechol exists as a catechol and / or as a semiquinone and / or as a quinone without the presence of a primary or secondary amine, and also includes both a reactive species separate from the catechol-containing polymer or oligomer and a catalyst, co-catalyst, or accelerator.

[0072] 1 shows a general schematic diagram of a layered HPF 100 comprising a catechol-containing material 20 coated onto an HPF 20 comprising a catechol-containing polymer or oligomer, and a catechol-containing material as described herein. The coated HPF 100 comprises an HPF core 10 and a catechol-containing material 20 coated onto the HPF 10.

[0073] The coated HPF 100 may also optionally include another polymer 30 disposed on and in contact with the catechol-containing material 20 coated on the HPF. The coated HPF 100 may also include a second catechol-containing material 40 coated on the HPF, comprising a catechol-containing polymer or oligomer, disposed on and in contact with the polymer 30. In one embodiment, the coated HPF 100 may also include a second polymer layer 50 disposed on and in contact with the second catechol-containing material 40 coated on the HPF. The polymer 30 or the second polymer 50 may be a catechol-containing polymer or oligomer, or another polymer.

[0074] In some embodiments, the catechol-containing polymer or oligomer in the catechol-containing material 20 coated on the HPF is an oligomer. In some embodiments, the catechol-containing polymer or oligomer in the catechol-containing material 20 coated on the HPF is a polymer.

[0075] In some embodiments, the catechol-containing material 20 coated on the HPF includes a reactive species separate from the catechol-containing polymer or oligomer, hi some embodiments, the reactive species is a urethane component, an epoxy resin, an acrylate monomer or oligomer, a methacrylate monomer or oligomer, a silane, or a combination thereof.

[0076] In some embodiments, the reactive species separate from the catechol-containing polymer or oligomer is a urethane component, hi some embodiments, the urethane component is a polyol or an organic compound containing multiple hydroxyl groups, and the urethane is linear or branched.

[0077] In some embodiments, the urethane component is 1,6-hexanediol, glycerol, Stepanpol PDC-279®, or polycaprolactone triol. In some embodiments, the urethane component is 1,6-hexanediol. In some embodiments, the urethane component is glycerol. In some embodiments, the urethane component is Stepanpol PDC-279®. In some embodiments, the urethane component is polycaprolactone triol.

[0078] In some aspects, the reactive species separate from the catechol-containing polymer or oligomer is an epoxy resin. In some embodiments, the epoxy resin is an epoxy monomer, an epoxy oligomer, a polyepoxide, or a combination thereof, where the epoxy is linear or branched. In some embodiments, the epoxy resin is an epoxy monomer. In some embodiments, the epoxy resin is an epoxy oligomer. In some embodiments, the epoxy resin is a polyepoxide.

[0079] In some embodiments, the epoxy resin is bisphenol A diglycidyl ether, bisphenol A epoxy resin, bis(4-glycidyloxyphenyl)methane, bisphenol E diglycidyl ether (DGEBE), 2,2′-[1,1-ethanediylbis(4,1-phenyleneoxymethylene)]dioxirane, bisphenol F diglycidyl ether (DGEBF), poly(bisphenol A-co-epichlorohydrin), or a combination thereof.

[0080] In some embodiments, the epoxy resin is bisphenol A diglycidyl. In some embodiments, the epoxy resin is bisphenol A epoxy resin. In some embodiments, the epoxy is bis(4-glycidyloxyphenyl)methane. In some embodiments, the epoxy resin is bisphenol E diglycidyl ether (DGEBE). In some embodiments, the epoxy resin is 2,2'[1,1-ethanediylbis(4,1-phenyleneoxymethylene)]dioxirane. In some embodiments, the epoxy resin is bisphenol F diglycidyl ether (DGEBF). In some embodiments, the epoxy resin is poly(bisphenol A-co-epichlorohydrin).

[0081] In some aspects, the reactive species separate from the catechol-containing polymer or oligomer is an acrylate monomer or oligomer. In some embodiments, the acrylate monomer or oligomer is an acrylate monomer comprising a vinyl group and at least one of a carboxylic acid ester and a carboxylic acid nitrile, and the acrylate is linear or branched.

[0082] In some embodiments, the acrylate monomer or oligomer is ethyl acrylate, ethylene-methyl acrylate, methyl methacrylate, 2-chloroethyl vinyl ether, 2-hydroxyethyl acrylate, hydroxyethyl methacrylate, butyl acrylate, trimethylolpropane triacrylate (TMPTA), or a combination thereof.

[0083] In some embodiments, the acrylate monomer or oligomer is ethyl acrylate. In some embodiments, the acrylate monomer or oligomer is ethylene-methyl acrylate. In some embodiments, the acrylate monomer or oligomer is methyl methacrylate. In some embodiments, the acrylate monomer or oligomer is 2-chloroethyl vinyl ether. In some embodiments, the acrylate monomer or oligomer is 2-hydroxyethyl acrylate. In some embodiments, the acrylate monomer or oligomer is hydroxyethyl methacrylate. In some embodiments, the acrylate monomer or oligomer is butyl acrylate. In some embodiments, the acrylate monomer or oligomer is trimethylolpropane triacrylate (TMPTA).

[0084] In some embodiments, the reactive species separate from the catechol-containing polymer or oligomer is a silane. In some embodiments, the reactive species separate from the catechol-containing polymer or oligomer is a methacrylate monomer or oligomer. In some embodiments, the reactive species separate from the catechol-containing polymer or oligomer is a methacrylate monomer. In some embodiments, the reactive species separate from the catechol-containing polymer or oligomer is a methacrylate oligomer.

[0085] In one embodiment, the catechol-containing material 20 coated on the HPF 10 includes a catalyst, co-catalyst, or accelerator, where the catalyst, co-catalyst, or accelerator is a urethane catalyst that promotes a urethane polymerization reaction, an epoxy catalyst that promotes an epoxy polymerization reaction, an acrylate catalyst that promotes an acrylate polymerization reaction, or a combination thereof.

[0086] In some embodiments, the catalyst, co-catalyst, or accelerator is a urethane catalyst that promotes the urethane polymerization reaction. In some embodiments, the urethane catalyst is an aliphatic amine catalyst, a cycloaliphatic amine catalyst, an alcohol amine catalyst, an aromatic amine catalyst, or an ether amine catalyst.

[0087] In some embodiments, the urethane catalyst is an aliphatic amine catalyst, hi some embodiments, the aliphatic amine catalyst is N,N-dimethylcyclohexane, triethylenediamine, N,N,N,N-tetramethylalkylenediamine, N,N,N,N-pentamethyldiethylenetriamine, triethylamine, N,N-dimethylbenzylamine, N,N-dimethylhexadecylamine, N,N-dimethylbutylamine, or a combination thereof.

[0088] In some embodiments, the urethane catalyst is a cycloaliphatic amine catalyst, ie, triethylenediamine, N-ethylmorpholine, N-methylmorpholine, N,N-diethylpiperazine, N,N-bis-(α-hydroxypropyl)-2-methylpiperazine, N-hydroxypropyldimethylmorpholine, or a combination thereof.

[0089] In some embodiments, the urethane catalyst is an alcohol amine catalyst. In some embodiments, the alcohol amine catalyst is triethanolamine or N,N-dimethylethanolamine.

[0090] In some embodiments, the urethane catalyst is an aromatic amine catalyst. In some embodiments, the aromatic amine catalyst is pyridine or N,N-dimethylpyridine.

[0091] In some embodiments, the urethane catalyst is an etheramine catalyst. In some embodiments, the etheramine catalyst is BDMAEE.

[0092] In some embodiments, the urethane catalyst is 1,4-diazabicyclo[2.2.2]octane, K-KAT 6212, benzyldimethylamine, or a combination thereof. In some embodiments, the urethane catalyst is 1,4-diazabicyclo[2.2.2]octane. In some embodiments, the urethane catalyst is K-KAT 6212. In some embodiments, the urethane catalyst is benzyldimethylamine.

[0093] In some embodiments, the catalyst, co-catalyst, or accelerator is an epoxy catalyst that promotes epoxy polymerization.

[0094] Suitable catalysts, cocatalysts, or accelerators are substances that promote the reaction between amino groups and epoxy groups, such as acids or compounds that can be hydrolyzed to acids. Suitable catalysts, cocatalysts, or accelerators include, but are not limited to, organic carboxylic acids such as acetic acid, benzoic acid, salicylic acid, 2-nitrobenzoic acid, and lactic acid; organic sulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid, and 4-dodecylbenzenesulfonic acid; sulfonic acid esters; other organic or inorganic acids such as phosphoric acid, or mixtures of the aforementioned acids and acid esters; nitrates, particularly calcium nitrate; or tertiary amines such as 1,4-diazabicyclo[2.2.2]octane, benzyldimethylamine, α-methylbenzyldimethylamine, triethanolamine, and dimethylaminopropylamine.

[0095] In some embodiments, the epoxy catalyst is acetic acid, benzoic acid, salicylic acid, 2-nitrobenzoic acid, lactic acid, methanesulfonic acid, p-toluenesulfonic acid, 4-dodecylbenzenesulfonic acid, sulfonic acid esters, phosphoric acid, calcium nitrate, 1,4-diazabicyclo-[2.2.2]octane, benzyldimethylamine, α-methylbenzyldimethylamine, triethanolamine, dimethylaminopropylamine, N,N-dimethylpiperidine, triethylenediamine, 2,4,6-tris(dimethylaminomethyl)phenol (DMP-30), benzyldimethylamine (BDMA), 2-(dimethylaminomethyl)phenol (DMP-10), N,N-dimethylbenzylamine, (dimethylaminomethyl)phenol, or a combination thereof.

[0096] In some embodiments, the epoxy catalyst is 1,4-diazabicyclo[2.2.2]octane.

[0097] In some embodiments, the catalyst, co-catalyst, or accelerator is an acrylate catalyst that accelerates acrylate polymerization. In some embodiments, the acrylate catalyst is an acrylic polymerization accelerator or a free radical polymerization accelerator.

[0098] In some embodiments, the acrylate catalyst is methyl 4-N,N-dimethylamino-phenylacetate. 4-N,N-dimethylamino-phenylacetate (MDMAPA), N,N-dimethylaminoglutethimide (OMAG), N,N-dimethyl-p-toluidine (OMPT), N,N-di-2-hydroxyethyl-p-toluidine (DHEPT), N,N-di-2-hydroxypropyl-p-toluidine (DHPPT), N,N-dimethyl-sym-xylidine (DMSX), N,N-bis(3-p-tolyloxy-2-hydroxypropyl)-m-xylidine (BTX), or a combination thereof.

[0099] In one embodiment, the catechol-containing polymer or oligomer in the catechol-containing material 20 coated on the HPF comprises polycatecholstyrene (PCS).

[0100] In one aspect, the catechol-containing material 20, such as PCS, coated on the HPF 10 has a thickness of about 5 nanometers to about 100 microns. In some embodiments, the catechol-containing material 20, such as PCS, coated on the HPF has a thickness of about 15 nanometers to about 50 microns. In some embodiments, the catechol-containing material 20, such as PCS, coated on the HPF has a thickness of about 15 nanometers to about 15 microns. In some embodiments, the catechol-containing material 20, such as PCS, coated on the HPF has a thickness of about 100 nanometers to less than about 5 microns. In some embodiments, the catechol-containing material 20, such as PCS, coated on the HPF has a thickness of about 150 nanometers to about 1.5 microns.

[0101] In some embodiments, the catechol-containing material 20, such as PCS, coated on the HPF has a diameter of about 10 nanometers to about 100 microns, or about 10 nanometers to about 100 nanometers, or about 100 nanometers to about 150 nanometers, or about 150 nanometers to about 200 nanometers, or about 200 nanometers to about 250 nanometers, or about 250 nanometers to about 300 nanometers, or about 300 nanometers to about 350 nanometers, or about 350 nanometers to about 400 nanometers, or about 400 nanometers to about 450 nanometers, or about 450 nanometers. The thickness of the film is from about 500 nanometers to about 550 nanometers, or from about 550 nanometers to about 600 nanometers, or from about 600 nanometers to about 650 nanometers, or from about 650 nanometers to about 700 nanometers, or from about 700 nanometers to about 750 nanometers, or from about 750 nanometers to about 800 nanometers, or from about 800 nanometers to about 850 nanometers, or from about 850 nanometers to about 900 nanometers, or from about 900 nanometers to about 950 nanometers, or from about 950 nanometers to about 1000 nanometers.

[0102] In some embodiments, the catechol-containing material 20, such as PCS, coated on the HPF has a thickness of about 1 micron to about 1.5 microns, or about 1.5 microns to about 5 microns, or about 5 microns to about 10 microns, or about 10 microns to about 15 microns, or about 15 microns to about 20 microns, or about 20 microns to about 25 microns, or about 25 microns to about 30 microns, or about 30 microns to about 35 microns, or about 35 microns to about 40 microns, or about 40 microns to about 50 microns. It has a thickness of about 45 microns, or about 45 microns to about 50 microns, or about 50 microns to about 55 microns, or about 55 microns to about 60 microns, or about 60 microns to about 65 microns, or about 65 microns to about 70 microns, or about 70 microns to about 75 microns, or about 75 microns to about 80 microns, or about 80 microns to about 85 microns, or about 85 microns to about 90 microns, or about 90 microns to about 95 microns, or about 95 microns to about 100 microns.

[0103] In some embodiments, the thickness of the aggregates of catechol-containing material, such as PCS, coated on high performance fiber (HPF) ranges from about 5 nanometers to about 10 microns. Stated differently, the thickness of the aggregates is any one number selected from the set of numbers below, or within a range defined by any two numbers measured in nanometers (including the endpoints of such ranges): 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, 100, ...200, ...300, ...400, 500, 600, 700, 800..., 900, ...1000, 2000, 3000, 4000, 5000, 6000, 7000, 8000, 9000, and 10000.

[0104] In some embodiments, the PCS contains about 5% to about 85% catechol. In some embodiments, the PCS contains about 10% to 75%, about 15% to 60%, or about 20% to about 40% catechol. In some embodiments, the PCS contains about 25% to about 35% catechol. In some embodiments, the PCS contains about 25% catechol. In some embodiments, the PCS contains about 35% catechol.

[0105] In some embodiments, the PCS contains from about 20% catechol to about 22% catechol, or from about 22% catechol to about 24% catechol, or from about 24% catechol to about 26% catechol, or from about 26% catechol to about 28% catechol, or from about 28% catechol to about 30% catechol, or from about 30% catechol to about 32% catechol, or from about 32% catechol to about 34% catechol, or from about 34% catechol to about 36% catechol, or from about 36% catechol to about 38% catechol, or from about 38% catechol to about 40% catechol.

[0106] In some embodiments, the PCS contains from about 5% catechol to about 85% catechol. Stated differently, the catechol content in the PCS is any one number selected from the set of numbers below, or within a range defined by any two numbers measured by weight content (including the endpoints of such ranges): 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, and 85.

[0107] In some embodiments, the catechol-containing material 20 coated on the HPF is a continuous layer. In some embodiments, the catechol-containing material 20 coated on the HPF is a discontinuous layer.

[0108] In some embodiments, the HPF 10 is wet. In some embodiments, the HPF 10 is dry. In some embodiments, the HPF 10 is semi-wet. In some embodiments, the HPF 10 is hydrous.

[0109] In some embodiments, the surface of the HPF 10 may be treated prior to placement of the coated catechol-containing material on the HPF. In some embodiments, the surface of the HPF 10 is anodized. In some embodiments, the surface of the HPF 10 is phosphate treated.

[0110] Embodiments of the present disclosure are described with respect to catechol-containing materials coated onto HPF.

[0111] In one aspect, the present disclosure is directed to a catechol-containing material 20 coated onto a HPF 10, which may also be in contact with another polymer 30, as described herein.

[0112] In some embodiments, polymer 30 comprises a polyester. In some embodiments, polymer 30 comprises a urethane. In some embodiments, polymer 30 comprises a phenolic. In some embodiments, polymer 30 comprises an epoxy, an acrylic, or a silane. In some embodiments, polymer 30 comprises an epoxy. In some embodiments, polymer 30 comprises an acrylic. In some embodiments, polymer 30 comprises a silane. In some embodiments, polymer 30 comprises a silicone.

[0113] In some embodiments, polymer 30 comprises one or more polymers listed in Table 1 below, as well as one or more polymers from the following list:

[0114] thermoplastic Polypropylene, polyethylene (high density and low density), polycarbonate, polyvinyl chloride (PVC), polyetheretherketone (PEEK), polyethersulfone (PES), polyphenylene sulfide (PPS), polyamide (nylon), polymethyl methacrylate (PMMA), polyetherimide (PEI), acetal (POM), sulfone polymers (PPSU, PSU), ethylene-vinyl acetate (EVA), liquid crystal polymer (LCP), polybutylene terephthalate (PBT), acrylonitrile butadiene styrene (ABS), fluoropolymers (PTFE, FEP), thermoplastic elastomers Elastomer (TPE), Thermoplastic Polyurethane (TPU), Polycyclohexylenedimethylene Terephthalate (PCT).

[0115] thermosetting material Epoxy resin, polyester resin, vinyl ester resin, phenolic resin, polyimide, polyurethane, polystyrene, silicone resin, cyanate ester, melamine-formaldehyde resin, polydicyclopentadiene (pDCPD), polyarylate (PAR), polybenzimidazole (PBI), polychlorotrifluoroethylene (PCTFE), methyl methacrylate-butadiene-styrene (MBS).

[0116] others Polyacrylonitrile (PAN), Polyhydroxyalkanoate (PHA), Bio-based polymers (PLA, PHB), Polyoxymethylene Copolymer (POM-C).

[0117] In some embodiments, polymer 30 is a continuous layer. In some embodiments, polymer 30 is a discontinuous layer.

[0118] In some embodiments, the catechol-containing material 20 and the polymer 30 form an interpenetrating polymer network (IPN), which as used herein is taken to mean at least two polymer networks that are at least partially entangled on a molecular scale but are not covalently bonded to each other and cannot be separated unless chemical bonds are broken.

[0119] In some embodiments, the catechol-containing material 20 and the polymer 30 form a semi-interpenetrating polymer network (SIPN). SIPN, as used herein, is understood to mean one or more polymer networks and one or more linear or branched polymers, characterized by molecular-scale penetration of at least one of the networks by at least some of the linear or branched macromolecules.

[0120] In some embodiments, the catechol-containing material 20 and the polymer 30 form a sequential interpenetrating polymer network (SeIPN). As used herein, SeIPN is intended to mean an interpenetrating polymer network prepared by a process in which a first component network is formed followed by the formation of a second component network.

[0121] In some embodiments, the catechol-containing material 20 and the polymer 30 form a sequential semi-interpenetrating polymer network (SSeIPN). As used herein, SSeIPN is intended to mean a polymer network prepared by a process in which linear or branched components are formed after completion of the reactions that result in the formation of the network, or vice versa.

[0122] In some embodiments, second polymer 50 is disposed on polymer 30. In some embodiments, second polymer 50 is disposed on and in contact with polymer 30. In some embodiments, second catechol-containing material 20 is disposed between polymer matrix 30 and second polymer 50.

[0123] V. Methods for Making HPFs Having a Coating of Catechol-Containing Material In one aspect, the present disclosure is directed to a method of making an HPF coated with a catechol-containing material, such as PCS, comprising disposing a catechol-containing material 20 described herein on the surface of an HPF 10. The method of disposing the catechol-containing material 20 described herein is not particularly limited and will be recognized by one of ordinary skill in the art.

[0124] In some embodiments, a method of making a coated HPF includes disposing a catechol-containing material 20 (e.g., in bulk) on the HPF 10 by spin coating, dip coating, spray coating, inkjet printing, flood coating, brushing, wiping, or the like. In some embodiments, the method includes disposing the catechol-containing material 20 on the high performance fiber 10 by spin coating. In some embodiments, the method includes disposing the catechol-containing material 20 on the high performance fiber 10 by dip coating. In some embodiments, the method includes disposing a polymer layer 20 on the high performance fiber 10 by spray coating. In some embodiments, the method includes disposing the catechol-containing material 20 on the high performance fiber 10 by inkjet printing. In some embodiments, the method includes disposing the catechol-containing material 20 on the high performance fiber 10 by flood coating. In some embodiments, the method includes disposing the catechol-containing material 20 on the high performance fiber 10 by brushing. In some embodiments, the method includes disposing the catechol-containing material 20 on the high performance fiber 10 by wiping.

[0125] In some embodiments, a method of making a high performance fiber includes disposing a catechol-containing material 20 on a high performance fiber 10, where the catechol-containing material 20 is applied to the high performance fiber 10 as a solution. In some embodiments, the solution includes from about 0.001% to about 10% by weight of a catechol-containing polymer or oligomer. In some embodiments, the solution includes from about 0.01% to about 5% by weight of a catechol-containing polymer or oligomer. In some embodiments, the solution includes from about 0.01% to about 1% by weight of a catechol-containing polymer or oligomer. In some embodiments, the solution includes from about 0.1% to about 1% by weight of a catechol-containing polymer or oligomer.

[0126] In some embodiments, the solution contains from about 0.001% to about 0.005% by weight of a catechol-containing polymer or oligomer, or from about 0.005% to about 0.01% by weight of a catechol-containing polymer or oligomer, or from about 0.01% to about 0.02% by weight of a catechol-containing polymer or oligomer, or from about 0.02% to about 0.03% by weight of a catechol-containing polymer or oligomer, or from about 0.03% to about 0.04% by weight of a catechol-containing polymer or oligomer, or from about 0.04% to about 0.05% by weight of a catechol-containing polymer or oligomer. a polymer or oligomer, or about 0.05% to about 0.06% by weight of a catechol-containing polymer or oligomer, or about 0.06% to about 0.07% by weight of a catechol-containing polymer or oligomer, or about 0.07% to about 0.08% by weight of a catechol-containing polymer or oligomer, or about 0.08% to about 0.09% by weight of a catechol-containing polymer or oligomer, or about 0.09% to about 0.1% by weight of a catechol-containing polymer or oligomer, or about 0.1% to about 0.11% by weight of a catechol-containing polymer or oligomer or oligomer, or about 0.11% to about 0.12% by weight of a catechol-containing polymer or oligomer, or about 0.12% to about 0.13% by weight of a catechol-containing polymer or oligomer, or about 0.13% to about 0.14% by weight of a catechol-containing polymer or oligomer, or about 0.14% to about 0.15% by weight of a catechol-containing polymer or oligomer, or about 0.15% to about 0.2% by weight of a catechol-containing polymer or oligomer, or about 0.2% to about 0.25% by weight of a catechol-containing polymer or oligomer. catechol-containing polymer or oligomer, or about 0.25% to about 0.3% by weight of a catechol-containing polymer or oligomer, or about 0.3% to about 0.35% by weight of a catechol-containing polymer or oligomer, or about 0.35% to about 0.4% by weight of a catechol-containing polymer or oligomer, or about 0.4% to about 0.45% by weight of a catechol-containing polymer or oligomer, or about 0.45% to about 0.5% by weight of a catechol-containing polymer or oligomer, or about 0.5% to about 0.75% by weight of a catechol-containing polymer or oligomer, or about 0.The composition contains 75% to about 1% by weight of a catechol-containing polymer or oligomer, or about 1.25% to about 1.5% by weight of a catechol-containing polymer or oligomer, or about 1.5% to about 1.75% by weight of a catechol-containing polymer or oligomer, or about 1.75% to about 2% by weight of a catechol-containing polymer or oligomer.

[0127] In some embodiments, the catechol-containing polymer or oligomer used in the solution is polycatecholstyrene (PCS). In some embodiments, the solution comprises about 0.001% to about 10% by weight of PCS. In some embodiments, the solution comprises about 0.01% to about 5% by weight of PCS. In some embodiments, the solution comprises about 0.01% to about 1% by weight of PCS. In some embodiments, the solution comprises about 0.1% to about 1% by weight of PCS.

[0128] In some embodiments, the solution contains about 0.001% to about 0.005% by weight PCS, or about 0.005% to about 0.01% by weight PCS, or about 0.01% to about 0.02% by weight PCS, or about 0.02% to about 0.03% by weight PCS, or about 0.03% to about 0.04% by weight PCS, or about 0.04% to about 0.05% by weight PCS, or about 0.05% to about 0.05% by weight PCS. % to about 0.06% by weight of PCS, or about 0.06% to about 0.07% by weight of PCS, or about 0.07% to about 0.08% by weight of PCS, or about 0.08% to about 0.09% by weight of PCS, or about 0.09% to about 0.1% by weight of PCS, or about 0.1% to about 0.11% by weight of PCS, or about 0.11% to about 0.12% by weight of PCS, or about 0.12% by weight about 0.13 wt% PCS, or about 0.13 wt% to about 0.14 wt% PCS, or about 0.14 wt% to about 0.15 wt% PCS, or about 0.15 wt% to about 0.2 wt% PCS, or about 0.2 wt% to about 0.25 wt% PCS, or about 0.25 wt% to about 0.3 wt% PCS, or about 0.3 wt% to about 0.35 wt% PCS, or about 0.35 wt% to about 0. Contains 4% by weight of PCS, or about 0.4% to about 0.45% by weight of PCS, or about 0.45% to about 0.5% by weight of PCS, or about 0.5% to about 0.75% by weight of PCS, or about 0.75% to about 1% by weight of PCS, or about 1.25% to about 1.5% by weight of PCS, or about 1.5% to about 1.75% by weight of PCS, or about 1.75% to about 2% by weight of PCS.

[0129] In some embodiments, the solution comprises a catechol-containing polymer or oligomer, such as PCS, in a weight percent described by the following number, or by a number within a range defined by any two of the following numbers, including the endpoints of such ranges: 0.001, 0.002, 0.003, 0.004, 0.005, 0.006, 0.007, 0.008, 0.009, 0.010, ..., 0.020, 0.030, 0.040, 0.050, 0.060, 0.070, 0.080, 0.090, 0.100, ..., 0.200, 0.300, 0.400, 0.500, 0.600, 0.700, 0.800, 0.900, 1.000, ..., 2.000, 3.000, 4.000, 5.000, 6.000, 7.000, 8.000, 9.000, and 10.000.

[0130] In some embodiments, the concentration of PCS-type catechol-containing material can be as high as 20%.

[0131] In some embodiments, the solution also includes an aqueous or organic solvent for dissolving the catechol-containing polymer or oligomer, hi some embodiments, the organic solvent is acetone, toluene, chloroform, dichloromethane (DCM), ethyl acetate, methyl ethyl ketone (MEK), or a combination thereof.

[0132] In some embodiments, the organic solvent is acetone. In some embodiments, the organic solvent is toluene. In some embodiments, the organic solvent is chloroform. In some embodiments, the organic solvent is dichloromethane (DCM). In some embodiments, the organic solvent is ethyl acetate. In some embodiments, the organic solvent is methyl ethyl ketone (MEK). In some embodiments, the organic solvent is a combination of acetone and toluene. In some embodiments, the organic solvent is acetone, and the catechol-containing polymer or oligomer is PCS. In some embodiments, the organic solvent is toluene, and the catechol-containing polymer or oligomer is PCS. In some embodiments, the organic solvent is a combination of acetone and toluene, and the catechol-containing polymer or oligomer is PCS.

[0133] The pH of the solution is not particularly limited. In some embodiments, the pH of the solution is about 3, or about 3.5, or about 4, or about 4.5, or about 5, or about 5.5, or about 6, or about 6.5, or about 7, or about 7.5, or about 8, or about 8.5, or about 9, or about 9.5, or about 10, or about 10.5, or about 11.

[0134] In some embodiments, the pH of the solution is about 3-3.5, or about 3.5-4, or about 4-4.5, or about 4.5-5, or about 5-5.5, or about 5.5-6, or about 6-6.5, or about 6.5-7, or about 7-7.5, or about 7.5-8, or about 8-8.5, or about 8.5-9, or about 9-9.5, or about 9.5-10, or about 10-10.5, or about 10.5-11.

[0135] In one embodiment, the molecular weight of the PCS monomer / oligomer / polymer ranges from as low as 4000 Da to as high as 1,000,000 Da. This does not exclude low molecular weight oligomers or high molecular weight polymers from being in accordance with the present disclosure.

[0136] In one embodiment, the molecular weight of the PCS material is any one of the following numbers in kilodaltons, as well as any number within the range defined by any two of the following numbers, inclusive of the endpoints: 0.2, 0.4, 0.6, 0.8, 1, 2, 3, 4, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, 310, 320, 330, 340, 350, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470, 480, 49 0, 500, 510, 520, 530, 540, 550, 560, 570, 580, 590, 600, 610, 620, 630, 640, 650, 660, 670, 680, 690, 700, 710, 720, 730, 740, 750, 760, 770, 780, 790, 800, 810, 820, 830, 840, 850, 860, 870, 880, 890, 900, 910, 920, 930, 940, 950, 960, 970, 980, 990, and 1000.

[0137] Obviously, the above ranges include the monomeric, oligomeric, and polymeric portions of the catecholstyrene.

[0138] VI. High Performance Fiber Reinformed Composite Polymer Structures In one embodiment, HPF coated with a catechol-containing sizing agent, such as PCS, of the present disclosure is used to prepare FRCP polymer structures and articles. Thermosetting and thermoplastic polymers are used as matrix materials as described below. Carbon fibers coated with a catechol-containing material, such as PCS, are then used in the following matrix to prepare fiber-reinforced composites.

[0139] [Table 1]

[0140] Examples of suitable plastic materials include thermoplastic polymers, thermosetting polymers, resins, and cross-linked resins, including, for example, polyphenylene sulfide (PPS) and polyetherketoneketone (PEKK). The thermoplastic polymer matrix material may include any one of a variety of suitable thermoplastic polymers, such as polypropylene (PP), polyethylene (PE), and polyvinyl chloride (PVC).

[0141] Some of the matrix resins that can be used as matrices for preparing fiber reinforced composites from the HPF of the present disclosure are as follows:

[0142] thermoplastic Polypropylene, polyethylene (high and low density), polycarbonate, polyvinyl chloride (PVC), polyetheretherketone (PEEK), polyethersulfone (PES), polyphenylene sulfide (PPS), polyamide (nylon), polymethyl methacrylate (PMMA), polyetherimide (PEI), acetal (POM), sulfone polymers (PPSU, PSU), ethylene-vinyl acetate (EVA), liquid crystal polymer (LCP), polybutylene terephthalate (PBT), acrylonitrile butadiene styrene (ABS), fluoropolymers (PTFE, FEP), thermoplastic elastomers (TPE), thermoplastic polyurethanes (TPU), polycyclohexylene dimethylene terephthalate (PCT).

[0143] thermosetting material Epoxy resin, polyester resin, vinyl ester resin, phenolic resin, polyimide, polyurethane, polystyrene, silicone resin, cyanate ester, melamine-formaldehyde resin, polydicyclopentadiene (pDCPD), polyarylate (PAR), polybenzimidazole (PBI), polychlorotrifluoroethylene (PCTFE), methyl methacrylate-butadiene-styrene (MBS).

[0144] others Polyacrylonitrile (PAN), polyhydroxyalkanoate (PHA), bio-based polymers (PLA, PHB), polyoxymethylene copolymer (POM-C).

[0145] VII. ARTICLES FROM FIBER-REINFORCED COMPOSITES (FRC) In one embodiment of the present disclosure, an article is prepared from the FRC described above.

[0146] In addition to coating individual carbon fibers, PCS-type materials can be used as thin-film primers for HPF fiber parts. In one embodiment, the part is immersed in a self-polymerizing bath of an oligomeric catechol-containing material, such as an oligomer of PCS, and allowed to polymerize, creating a layer of PCS on the carbon fiber surface. Alternatively, a polymeric PCS in solution form, as described in this disclosure, can be used to dip-coat or spray-coat parts or articles formed from the HPF fibers of the present disclosure. Stated differently, in one embodiment, the present disclosure relates to preparing a part from the HPF fibers described herein and coating such a part with a PCS-type material in solution (dissolved in a solvent such as acetone).

[0147] In one embodiment of the present disclosure, a fiber-reinforced composite polymer is prepared from one or more HPF fibers described herein, either coated or uncoated with a PCS-type coating material, and the matrix is ​​one or more matrix polymers and resins described herein. Articles are made from such fiber-reinforced composite polymers.

[0148] In one embodiment, the present disclosure provides a method for applying a coating (sizing with and without a PCS-type material) to at least one surface of a substrate made from a fiber-reinforced thermoplastic composite material described herein, the method comprising a first step of applying a PCS-type layer, optionally filled with graphene or zinc particles, to the surface of the substrate as a primer, and then a second step of applying a coating to the zinc or graphene particle-filled adhesive PCS-type layer.

[0149] The use of a PCS type layer provides a high level of adhesion between the substrate and the coating, despite the low surface energy of the fiber reinforced thermoplastic composite substrate.

[0150] The adhesive PCS type layer has a thickness of 100 nm to 100 μm, and the adhesive PCS type layer is filled with graphene and contains 0.5 wt % to 2 wt % graphene.

[0151] The present disclosure also provides a substrate, such as an aircraft part, comprising a coating on at least one surface, the substrate comprising a zinc or graphene particle-filled adhesive PCS-type layer as a primer interposed between the surface of the substrate and the coating.

[0152] According to one embodiment, the panel is made from FRC material, for example, the panel comprises carbon fibers embedded in a thermoplastic resin matrix of the PEEK, PEKK, PAEK or PPS type.

[0153] The coating comprises at least one paint or protective layer. According to one embodiment, the coating comprises at least one anticorrosion layer, at least one paint layer, and at least one varnish layer. These different layers are applied in the same manner as in the prior art.

[0154] According to one procedure, the application method comprises, after a preparation step on the surface of the substrate, such as degreasing, applying an adhesive PCS-type layer, which can be applied to the surface of the substrate in a non-aqueous solution, for example by spray coating or dip coating.

[0155] According to one embodiment, the adhesive PCS-type layer is filled with graphene particles. The adhesive PCS-type layer contains 0.5% to 2% by weight of graphene. In one configuration, the graphene particles are present in the form of platelets. Thanks to the graphene present, the adhesive PCS-type layer is electrically and thermally conductive. The graphene present also confers anti-corrosion properties to the layer.

[0156] According to one embodiment, the adherent PCS type layer is filled with zinc particles to provide corrosion protection properties and to provide a corrosion barrier that is neither chromium nor cadmium-containing. In this embodiment, the adherent PCS layer contains 0.5% to 2% zinc by weight.

[0157] The use of an adhesive PCS-type layer provides a high level of adhesion between the substrate and the coating, despite the low surface energy of the thermoplastic composite substrate, without the need for surface treatments such as plasma treatment.

[0158] When the adhesive PCS-type layer is filled with graphene, it forms a lightning protection layer that can supplement or replace another lightning protection layer, such as a metal mesh. Adding graphene to the adhesive PCS-type layer is more effective than adding the same amount of graphene to the PCS to obtain a lightning protection layer, because the thickness of the adhesive PCS-type layer is significantly thinner than the thickness of the coating, making it possible to obtain a higher concentration of graphene.

[0159] According to one embodiment, a prior art composite panel coated with a first coating includes a metal mesh interposed between the panel and the first coating, forming a lightning protection layer. Such panels may have damaged areas on their surfaces where the metal mesh and first coating are no longer present. According to another advantage of the present invention, such panels can be repaired by coating the damaged areas with a graphene particle-filled adhesive PCS-type layer and then with a second coating. After repair, the adhesive PCS-type layer in contact with the metal mesh ensures the continuity of the lightning protection layer, and the second coating ensures the continuity of the first coating. [Example]

[0160] experiment Example 1: Aramid Fiber as a High Performance Fiber As described above, the present disclosure relates to high performance fibers (HPF), such as HPP (high performance polymer) fibers coated with polycatecholstyrene (PCS). In this experiment, raw aramid fiber (AF; 25 g) was placed in a glass reactor. 1 L of acetone was added to the reactor and stirred for 1 hour to wash the aramid fiber.

[0161] The fibers were functionalized by separating a portion of the fibers, drying them, and placing the remainder in 1 L of acetone containing 60 g of ZnCl solution and stirring for 6 hours to disrupt the hydrogen bonds of the fibers (not wishing to be bound by this theory, we speculate). A portion of the fibers was separated, drying them, and placing the remainder in 1 L of acetone containing 5 g of PCS and stirring for 1 hour.

[0162] Fibers were filtered from each solution using vacuum filtration, and the filtered fibers were rinsed with 1x phosphate buffer saline (PBS) and isopropyl alcohol to remove any residue, unbound PCS, and debris not attached to the fibers.

[0163] After drying in a vacuum chamber at 25°C, the fibers were analyzed using SEM. Visual inspection under magnification revealed that the fibers had a thin film coating. The resulting SEM images are shown below in Figures 2A-2C, 2D-2F, and 2G-2I. Figures 2A-2C depict lower magnifications, Figures 2D-2F depict higher magnifications, and Figures 2G-2I depict the highest magnification used as shown in the SEM. Figures 2A, 2D, and 2G depict washed aramid fibers. Figures 2B, 2E, and 2H depict ZnCl-treated washed aramid fibers, and Figures 2C, 2F, and 2I depict aramid fibers subsequently coated with ZnCl and PCS.

[0164] This disclosure relates to individual aramid fibers that have been coated with a thin poly(catecholstyrene) (PCS) film. This thin polymer film functionalizes the previously inert aramid fiber surface with catechol moieties that can aid in adhesion to the matrix of various thermoset and thermoplastic composite materials. In one embodiment, the coating method involves simply stirring raw aramid fibers in an organic solvent containing dissolved PCS. The PCS in solution forms bonds with the aramid fiber surface, leaving behind a deposited thin film. Following this coating reaction, the fibers are filtered, rinsed with isopropyl alcohol and DI water, and dried in a vacuum chamber to remove any residual solvent.

[0165] This one-step coating process offers advantages over many other coating processes. Previous AF coatings using mussel-inspired materials (specifically polydopamine) require a self-polymerization reaction to occur. This reaction is difficult to manage and control and is not easily scalable. The advantage of PCS is that it is prepolymerized; therefore, the coating process simply involves interacting a preformed catechol-containing polymer with the aramid fiber surface. Current experiments are being carried out at room temperature with a 5:1 weight ratio of AF to PCS in an acetone bath.

[0166] In one embodiment, the present disclosure relates to individual and multiple HPP fibers that are coated with a thin poly(catecholstyrene) (PCS) film. This thin polymer film functionalizes the previously inert carbon fiber surface with catechol moieties, which can aid in adhesion to the matrix of various thermoset and thermoplastic composite materials. The coating method involves stirring raw carbon fibers in an organic solvent containing dissolved PCS. The PCS from the solution forms bonds with the carbon fiber surface, leaving a deposited thin film. Following the coating reaction, the fibers are filtered, rinsed with isopropyl alcohol and DI water, and dried, preferably in a vacuum chamber, to remove any residual solvent.

[0167] This one-step coating process has advantages over many other coating processes. An advantage of PCS is that it is prepolymerized, so in one embodiment of the coating process, a preformed catechol-containing polymer interacts with the carbon fiber surface.

[0168] The current experiments were carried out at room temperature with a weight ratio of HPP fiber to PCS in an acetone bath of 5:1. Coating process variables such as temperature, inert atmosphere, addition of oxidizer, and various material ratios can be adjusted to provide a more optimized coating of the fiber.

[0169] These coated fibers are incorporated into a composite matrix to create a fiber-reinforced material.

[0170] Coating Process In the first step, 25g of raw chopped alamide fiber was added to a 4 liter reaction flask. 1 liter of acetone was added to the reaction flask. ·AF and acetone were stirred in a sealed reaction flask at room temperature for 1 hour. A portion of the fibers was separated and dried, and the remainder was placed in a reaction flask with 1 liter of acetone and 60 g of ZnCl2. ·AF was stirred in a sealed reaction flask in a 6% ZnCl2 bath at room temperature for 6 hours. A portion of the fibers was separated and dried, and the remainder was placed in a reaction flask with 1 liter of acetone and 5 grams of PCS, which was dissolved in an organic solvent. ·AF was stirred in a sealed reaction flask in a 0.5% PCS bath at room temperature for 1 hour. The fibers were filtered from the liquid medium and rinsed with 1x phosphate buffered saline followed by isopropanol to remove any free PCS and other debris. The fibers were analyzed under SEM and images 2A-2I were taken.

[0171] Figure 2 shows SEM micrographs of uncoated aramid fibers (2A, 2D, 2G), fibers treated with a 6% ZnCl bath (2B, 2E, 2H), and fibers treated with a ZnCl bath and PCS coating (2C, 2F, 2I). (2A, 2D, 2G) The aramid fibers were washed in an acetone bath for 1 hour. (2B, 2E, 2H) are portions of washed aramid fibers agitated in a 6% ZnCl bath for 6 hours. (2C, 2F, 2I) The aramid fibers were agitated in a 0.5% PCS bath for 1 hour. The PCS-coated fibers were then washed with 1x phosphate-buffered saline and then isopropanol to remove any unbound PCS from the fibers. (I) PCS can be seen adhering to and coating the individual aramid fibers. The ZnCl2 bath is necessary to break the hydrogen bonds formed between the aramid fibers themselves, thus improving the surface modification ability of the fibers and allowing the sites to form new hydrogen bonds. The extensive coating on the aramid fibers is most likely the result of hydrogen bonds created between the aramid fibers and the functional catechol groups of the PCS. Panels 2D and 2G are 250x and 2Kx magnifications of Panel 2A at 50x magnification, respectively. Panels 2E and 2H are 250x and 2Kx magnifications of Panel 2B at 60x magnification, respectively. Panels 2F and 2I are 250x and 2Kx magnifications of Panel 2C at 60x magnification, respectively. The scale bars for Panels 2A, 2B, and 2C are 200 microns; Panels 2D, 2E, and 2F are 100 microns; and Panels 2G, 2H, and 2I are 10 microns.

[0172] It was surprising that a polymer coating was obtained by simply stirring dissolved PCS with raw aramid fibers in an organic solvent. The fact that no heat or other reactants were required to stimulate a reaction between the materials appears to indicate the strong affinity that PCS has for the aramid fiber surface.

[0173] The HPP fibers can be chopped strands and can be any of the polymer types polyaramid, polyester, and UHMWPE. The length of the HPP fiber chopped strands is not critical, but in one embodiment, it is 5 microns to 50 mm. The diameter and number of filaments constituting the HPP fiber chopped strands are also not critical, but in one embodiment, the diameter is typically 500 nm to 50 microns. The number of filaments is typically 100 to 100,000. A sizing agent can be applied to the HPP fiber chopped strands beforehand.

[0174] Example 2: Carbon fiber as a high performance fiber As previously described, this disclosure relates to carbon fibers (CF) coated with polycatecholstyrene (PCS). In this experiment, raw carbon fibers (25 g) were placed in a glass reaction vessel. 1 L of acetone and 4 g of poly(catecholstyrene) were added to the reactor. The mixture was stirred at room temperature using an overhead stirrer for 24 hours. The fibers were filtered from the solution using vacuum filtration. The filtered fibers were rinsed with isopropyl alcohol and deionized water to remove any residue and debris not adhered to the fibers.

[0175] After drying in a vacuum chamber at 25°C, the fibers were analyzed using SEM. Visual inspection under magnification revealed that the fibers had a thin film coating on the carbon fibers. The resulting SEM images are provided in Figures 3A, 3B, and 3C, which correspond to magnifications of 7Kx, 2x, and 700x, respectively. Figure 4 shows SEM images of both untreated Teijin Tenax chopped fibers and PCS-coated chopped fibers.

[0176] Coating Process The current experiments were carried out at room temperature with a 5:1 weight ratio of CF:PCS in an acetone bath. Coating process variables such as temperature, inert atmosphere, addition of oxidizer, and various material ratios can be adjusted to provide a more optimized coating of the fibers. These coated fibers are then incorporated into a composite matrix to create a fiber-reinforced material.

[0177] The coating process is described in the following steps. In the first step, 25 grams of raw chopped carbon fiber was added to a 4 liter reaction flask. · Then 1 liter of acetone was added to the reaction flask. In the next step, 5 grams of PCS was added to the acetone / carbon fiber mixture. The PCS was dissolved in an organic solvent. The combined contents of the reaction flask were stirred in a sealed reaction flask at room temperature for 24 hours. The fibers were filtered from the liquid medium and rinsed with isopropanol followed by deionized water to remove any free PCS and other debris. The fibers were analyzed under SEM and the images shown in Figures 3A, 3B, and 3C were taken.

[0178] It was surprising that a polymer coating was obtained by simply stirring dissolved PCS with raw carbon fiber in an organic solvent. The fact that no heat or other reactants were required to stimulate a reaction between the materials appears to indicate the strong affinity that PCS has for the carbon fiber surface.

[0179] Example 3: Carbon fiber as a high performance fiber The purpose of this experiment was to test the effectiveness / performance of poly(catecholstyrene) (PCS)-coated carbon fiber. A very thin coating (or sizing) of PCS on carbon fiber enhances the interfacial adhesion between the fiber and resin used in reinforced plastic composites, increasing interfacial shear strength (IFSS). This is the case for both thermoset and thermoplastic resin systems. Furthermore, the improved fiber / resin interfacial adhesion leads to improved material properties of the resulting composite, such as increased flexural strength / modulus and increased compressive strength / modulus.

[0180] [Table 2]

[0181] The carbon fibers coated with a catechol-containing material such as PCS are then used in the following matrix to prepare fiber-reinforced composites:

[0182] [Table 3]

[0183] The Ecodyst system was used for large-scale batch coating of carbon fiber. The first fiber to be coated was recycled chopped carbon fiber from R&M. Approximately 18 liters of acetone was added to Ecodyst along with 90 g of PCS. For this coating, PCS32, with a Mw of 150,000 g / mol, was used. After the PCS was completely dissolved in the acetone, 250 g of carbon fiber was added. The carbon fiber was then stirred for one hour, after which the PCS solution was drained and collected for future batches. The carbon fiber was then spread on a large cookie sheet and left to dry overnight under a fume hood to remove any excess acetone. This process was repeated until 2 kg of carbon fiber was coated, with the PCS solution being completely replaced after each kg of carbon fiber was coated.

[0184] Figure 4 shows carbon fibers coated with PCS. SEM micrographs of carbon fibers without (Figures 4A, 4C, and 4E) or with (Figures 4B, 4D, and 4F) a PCS coating are shown. In Figures 4A, 4C, and 4E, the carbon fibers were washed in an acetone bath for 1 hour. Figures 4B, 4D, and 4F show a portion of the washed carbon fibers that had been stirred in a 0.5% PCS bath for 1 hour. The PCS-coated fibers were then washed with 1x phosphate-buffered saline and then isopropanol to remove any unbound PCS from the fibers. In Figure 4F, it can be seen that PCS has adhered to and coated individual carbon fibers. Figures 4C and 4E are 800x and 2Kx magnifications of Figure 4A at 50x magnification, respectively. Figures 4D and 4F are 800x and 2Kx magnifications of Figure 4B at 60x magnification, respectively. The scale bars in Figures 4A and 4B are 200 microns, those in Figures 4C and 4D are 20 microns, and those in Figures 4E and 4F are 10 microns.

[0185] Example 4: Recycled carbon fiber as a high performance fiber Recycled carbon fibers were coated with PCS. SEM micrographs of recycled carbon fibers are provided in Figure 5. (Figures 5A and 5C) show recycled carbon fibers that had been washed with acetone; a residual coating, likely epoxy, appeared to remain on the fibers. Figures 5B and 5D show recycled carbon fibers that had been treated with a poly(catecholstyrene) (PCS) coating. The PCS-coated fibers appeared to have a thicker and more pronounced coating than the residual coating on the recycled carbon fibers. The fibers were washed in an acetone bath, agitated in a 0.5% PCS solution for 1 hour, and then rinsed in an isopropyl alcohol bath to remove any unbound PCS. Figures 5C and 5D are 3Kx magnifications of Figures 5A and 5B, respectively, at 250x magnification. The scale bars in Figures 5A and 5B are 200 microns, and those in Figures 5C and 5D are 10 microns.

[0186] Furthermore, it has been shown that the fiber coating thickness can be adjusted by varying the concentration of PCS in the coating bath. However, the optimal coating thickness for improved IFSS and composite performance has yet to be determined. Figure 2 illustrates the effect of varying the concentration of PCS in the coating bath.

[0187] Example 5: PCS coating thickness can be controlled by polymer concentration. SEM micrographs of poly(catecholstyrene) (PCS)-coated recycled carbon fibers are shown in Figures 6A-6D. In Figures 6A and 6C, a 0.5% PCS solution was used to coat the fibers, which provided good coverage of the fibers. In Figures 5B and 5D, a 3% PCS solution was used to coat the fibers, which heavily coated the fibers with a thick PCS coating. These data demonstrate that the PCS coating thickness can be controlled based on the concentration of the polymer solution. The fibers were washed in an acetone bath and agitated in either a 0.5% or 3% PCS solution for 1 hour, then rinsed in an isopropyl alcohol bath to remove any unbound PCS. Figures 6C and 6D are 3Kx magnifications of Figures 6A and 6B at 250x magnification, respectively. The scale bars in Figures 6A and 6B are 200 microns, and those in Figures 6C and 6D are 10 microns.

[0188] The fibers used herein were recycled carbon fibers containing significant amounts (5-14%) of residual resin (believed to be epoxy). Nevertheless, it is clear that PCS coating thickness varies with the concentration of polymer in the coating bath. It is also important to note that the PCS concentration numbers (0.5% and 3%) refer to the weight percent of PCS in the acetone bath, not the resulting weight percent of coating added to the carbon fiber.

[0189] Example 6: Poly(catecholstyrene) as a sizing agent for carbon fiber reinforced composites In this example, PCS is used as a carbon fiber sizing agent on the performance of composite properties. The performance of PCS sizing agents varies depending on the resin system. An epoxy resin system is used in this study. Carbon fiber tows and fabrics are coated with PCS using dip coating. PCS sizing thickness and its weight concentration (while varying the dip bath concentration) relative to the carbon fiber material are quantified. Laminates are constructed from PCS-sized tows and / or fabrics. The impact of PCS sizing on composite properties is evaluated in terms of tensile strength / modulus, flexural strength / modulus, and compressive strength / modulus. The performance of composites constructed with PCS sizing agents is compared to composites constructed using both as-received fabric (with sizing agent applied) and desized fabric. This allows for a clear evaluation of the impact of PCS sizing on composite properties. Dip coating is used to prepare PCS-sized carbon fiber fabrics and tows. Because PCS is not water-soluble, a suitable solvent is selected for the coating process. For example, acetone is used for coating application. The dip coating process is optimized to control the PCS sizing addition, which is controlled by the PCS concentration in the coating bath and the residence time of the fibers in the coating solution.

[0190] Three different "levels" of PCS sizing addition (e.g., 0.5%, 1%, and 1.5% mass addition of PCS to the fiber material) are selected. The various sized carbon fiber fabrics are used to fabricate multilayer laminates for material property testing purposes. Laminates are also fabricated using as-received fabric (with standard sizing) and unsized fabric for experimental control purposes. An appropriate epoxy resin is used across all composite samples. After fabrication, the panels are cut to produce test specimens for testing.

[0191] The following material properties are evaluated for the test samples: Tensile strength and modulus ·Flexural strength and elastic modulus Compressive strength and elastic modulus

[0192] Material property data from PCS sized samples are compared to control samples to assess the impact on overall material properties.

[0193] To test for increased laminate bond strength, lap shear tests are performed on composite laminates bonded with epoxy 250°F curing adhesives. Tests are performed on baseline samples without surface preparation and on samples with surface preparation. Samples are also prepared with 1% additive brushed onto the surface, both without and with preparation. In one test, rubber sheeting is bonded onto the bismaleimide laminate surface with various adhesives at elevated temperatures and room temperature. Peel strength is measured. In one evaluation, paint adhesion tests are performed on polyetheretherketone (PEEK) laminates.

[0194] Two samples of polycatecholstyrene are used for sizing the carbon fibers. The first sample has a molecular weight of 240 KDa, and the second sample has a molecular weight of 110 KDa. The carbon fibers used are laid up in a 0° / 90° biaxial orientation. Sized and unsized fibers are preformed. Dip-coating solutions of PCS are prepared in acetone at concentrations of 0.5 wt%, 1.0 wt%, 1.5 wt%, and 2 wt%. Composite panels are fabricated from the sized and unsized fibers. A two-layer configuration of Chomarat® Carbon Fiber (0 / 90) (Chomarat North America, SC) is used. The carbon fibers (Figure 7A) are immersed in a solution (Figures 7B and 7C), e.g., 0.5 g of polymer in 99.5 g of acetone, for 5, 15, and 30 minutes. The samples are air-dried for 24 hours (Figure 7D).

[0195] The MP peak appears after 30 minutes of dip coating. The OH stretching peak occurs at a wavenumber of 3300-3400 cm. -1 Not detected in the vicinity. See Table 3 below and Figure 7-1.

[0196] [Table 4]

[0197] Figures 7E, 7F, and 7G show two layers of as-received Chomarat® carbon fibers (0 / 90) at three different magnifications. These fibers were not treated, and some sizing is visible in the SEM before burn-off. To remove the sizing already present in the as-received carbon fibers, they were burned in a furnace at 400°C for 1 hour. Figure 7H shows the carbon fibers before burn-off, and Figures 7I and 7J are the carbon fibers after burn-off. Figures 7K, 7L, and 7M are SEM micrographs of the carbon fibers after furnace burn-off. As can be seen, the carbon fibers are now unsized.

[0198] FTIR was performed on a ThermoScientific Nicolet iS50 FT-IR spectrometer (mid-IR region (5000–400 cm)). -1 The infrared absorption spectrum is measured in the 4000-400 cm region using a 240K polymer sample and a carbon fiber coated with 240K polymer as a sizing. -1 and the number of scans was 64.

[0199] Figure 8 shows the FTIR scans of the as-received and burned-off carbon fibers. Both the as-received and unsized carbon fibers are dip-coated with a 240K PCS solution in acetone.

[0200] 9A, 9B, and 9C are SEMs of as-received carbon fibers coated with a 0.5% PCS polymer solution in acetone that was dip coated for 30 minutes.

[0201] 10A, 10B, and 10C are SEMs of as-received carbon fibers coated with a 1.0% PCS polymer solution in acetone that was dip coated for 30 minutes.

[0202] Figure 11 shows the FTIR scans of as-received carbon fibers coated with 1% PCS in acetone solvent by dip coating for 5, 15, and 30 minutes. The PCS used is a 240K Dalton molecular weight material.

[0203] 12A, 12B, and 12C are SEMs of as-received carbon fibers coated with a 1.5% PCS polymer solution in acetone that has been dip coated for 5 minutes.

[0204] 13A, 13B, and 13C are SEMs of as-received carbon fibers coated with a 1.5% PCS polymer solution in acetone that has been dip coated for 15 minutes.

[0205] 14A, 14B, and 14C are SEMs of as-received carbon fibers coated with a 1.5% PCS polymer solution in acetone that has been dip coated for 30 minutes.

[0206] Figure 15 shows the FTIR scans of as-received carbon fibers coated with 1.5% PCS in acetone solvent by dip coating for 5, 15, and 30 minutes. The PCS used is a 240K Dalton molecular weight material.

[0207] 16A, 16B, and 16C are SEMs of as-received carbon fibers coated with a 2.0% PCS polymer solution in acetone that has been dip coated for 5 minutes.

[0208] Figures 17A, 17B, and 17C are SEMs of as-received carbon fibers coated with a 2.0% PCS polymer solution in acetone that has been dip coated for 15 minutes.

[0209] Figures 18A, 18B, and 18C are SEMs of as-received carbon fibers coated with a 2.0% PCS polymer solution in acetone that has been dip coated for 30 minutes.

[0210] Figure 19 shows the FTIR scans of as-received carbon fibers coated with 2.0% PCS in acetone solvent by dip coating for 5, 15, and 30 minutes. The PCS used is a 240K Dalton molecular weight material.

[0211] Figure 20A shows the top view of the carbon fiber after dip coating at 5, 15, and 30 minutes, and Figure 20B shows the bottom view of the carbon fiber after dip coating at 5, 15, and 30 minutes.

[0212] FIG. 21 shows carbon fibers that have been sized with PCS via dip coating and then used to make a laminate with a PEEK matrix.

[0213] It was found that for 1.5 wt % and 2 wt % dip coating using 240 KDalton PCS in acetone, clear peaks and sizing were observed on the CF (as received).

[0214] Similarly, unsized carbon fibers (as received, burned off) were also coated with 0.5, 1.0, 1.5, and 2.0% PCS solutions in acetone. Both molecular weights of PCS were used to form dip coating solutions.

Claims

1. Coated high-performance fibers (HPFs), wherein the HPFs are coated with a catechol-containing material comprising a polymer containing catechol, semiquinone, or quinone.

2. The coated HPF according to claim 1, wherein the catechol-containing material coated on the HPF comprises monomers, oligomers, or polymer catechol or catechol-containing material, wherein the catechol exists as catechol and / or as semiquinone and / or quinone without the presence of an amine, and the polymer layer optionally comprises at least one of a) a reactive species separate from the catechol or catechol-containing material, and b) a catalyst, co-catalyst, or accelerator.

3. The coated HPF according to claim 1, wherein the polymer material comprises a reactive species separate from the catechol-containing polymer or oligomer, the reactive species being a urethane component, epoxy resin, acrylate monomer or oligomer, methacrylate monomer or oligomer, silane, or a combination thereof.

4. The aforementioned reactive species (i) Urethane component, (ii) A urethane component which is a polyol or an organic compound containing a plurality of hydroxyl groups, wherein the urethane is linear or branched. (iii) Urethane component, which is 1,6-hexanediol, glycerol, Stepanpol PDC-279 (registered trademark), or polycaprolactone triol. (iv) epoxy resin, (v) An epoxy resin which is an epoxy monomer, epoxy oligomer, polyepoxide, or a combination thereof, wherein the epoxy is linear or branched, (vi) Bisphenol A diglycidyl ether, bisphenol A epoxy resin, bis(4-glycidyloxyphenyl)methane, bisphenol E diglycidyl ether (DGEBE), 2,2'-[1,1-ethanediylbis(4,1-phenyleneoxymethylene)]dioxirane, bisphenol F diglycidyl ether (DGEBF), poly(bisphenol A-co-epichlorohydrin), or combinations thereof, epoxy resin. (vii) Acrylate monomer or oligomer, (viiii) An acrylate monomer or oligomer comprising a vinyl group and at least one of a carboxylic acid ester and a carboxylic acid nitrile, wherein the acrylate is linear or branched, or The coated HPF according to claim 3, which is an acrylate monomer or oligomer, which is (ix) ethyl acrylate, ethylene-methyl acrylate, methyl methacrylate, 2-chloroethyl vinyl ether, 2-hydroxyethyl acrylate, hydroxyethyl methacrylate, butyl acrylate, trimethylolpropane triacrylate (TMPTA), or a combination thereof.

5. The coated HPF according to claim 1, wherein the polymer layer comprises the catalyst, co-catalyst, or accelerator, and the catalyst, co-catalyst, or accelerator is a urethane catalyst that promotes a urethane polymerization reaction, an epoxy catalyst that promotes an epoxy polymerization reaction, an acrylate catalyst that promotes an acrylate polymerization reaction, or a combination thereof.

6. The catalyst, co-catalyst, or accelerator is (i) A urethane catalyst that promotes the urethane polymerization reaction, (ii) A urethane catalyst that promotes the urethane polymerization reaction, which is 1,4-diazabicyclo[2.2.2]octane, K-KAT 6212, benzyldimethylamine, or a combination thereof. (iii) Epoxy catalyst that promotes epoxy polymerization, (iv) 1,4-diazabicyclo[2.2.2]octane epoxy catalyst, (v) an acrylate catalyst that promotes acrylate polymerization, or (vi) The coated HPF according to claim 5, wherein the acrylate catalyst is an acrylic polymerization accelerator or a free radical polymerization accelerator.

7. The coating of the aforementioned polymer material (i) Approximately 5 nanometers to approximately 100 microns, (ii) Approximately 15 nanometers to approximately 50 microns, (iii) Approximately 15 nanometers to approximately 15 microns, (iv) Approximately 50 nanometers to less than approximately 15 microns, (v) The coated HPF according to claim 1, having a thickness of about 50 nanometers to about 1.5 microns.

8. The coated HPF according to claim 1, wherein the catechol-containing polymer or oligomer comprises polycatecholstyrene (PCS).

9. The coated HPF according to claim 1, wherein the molecular weight is in the range of 100 to 1,000,000.

10. The coated HPF according to claim 8, wherein the PCS contains about 15% to about 85% catechol.

11. The coated HPF according to claim 10, wherein the PCS comprises about 25% catechol or about 35% catechol.

12. The coated HPF according to claim 1, wherein the HPF is a polymer.

13. The coated HPF according to claim 1, wherein the HPF is aramid, superaramid, aramid copolymer, metharamid, LCP, UHMWPE polymer, polyamide, polyester, polyolefin, or a combination thereof.

14. A fiber-reinforced composite material comprising one or more HPFs as described in claim 13.

15. The coated high-performance fiber (HPF) according to claim 1, wherein the HPF is a carbon fiber.

16. A fiber-reinforced composite material comprising HPF fibers as described in claim 15.

17. The matrix polymer A fiber-reinforced composite material according to claim 14 or 16, selected from polypropylene, polyethylene, polycarbonate, polyvinyl chloride, polyetheretherketone, polyethersulfone, polyphenylene sulfide, polyamide, polymethyl methacrylate, polyetherimide, acetal, sulfone polymer, ethylene-vinyl acetate, liquid crystal polymer, polybutylene terephthalate, acrylonitrile butadiene styrene, fluoropolymer, thermoplastic elastomer, thermoplastic polyurethane, polycyclohexylenedimethylene terephthalate, epoxy resin, polyester resin, vinyl ester resin, phenolic resin, polyimide, polyurethane, polystyrene, silicone resin, cyanate ester, melamine-formaldehyde resin, polydicyclopentadiene, polyarylate, polybenzimidazole, polychlorotrifluoroethylene, methyl methacrylate-butadiene-styrene, polyacrylonitrile, polyhydroxyalkanoate, polylactic acid, polyhydroxybutalate, and polyoxymethylene copolymer.

18. A method for preparing HPF according to claim 13 or 15, wherein the method comprises exposing the HPF to a prepolymerized catechol-containing polymer dissolved in one or more solvents.

19. A method for functionalizing the surface of an HPF according to claim 13 or 15, comprising exposing the HPF to a prepolymerized catechol-containing polymer dissolved in one or more solvents.

20. The coated HPF according to claim 13 or 15, wherein the HPF is completely or partially coated with a material containing a PCS polymer.

21. A manufactured article comprising the fiber-reinforced composite material according to claim 14 or 16.

22. A method for applying a coating to at least one surface of a substrate made from a fiber-reinforced composite material according to claim 14 or 16, wherein the method is: Applying a PCS layer filled with graphene or zinc particles as a primer to at least one surface of the substrate, A method comprising applying a coating to the zinc or graphene particle-filled PCS layer.

23. The zinc or graphene particle-filled adhesive PCS layer has a thickness of 200 nm to 100 μm, and / or The method according to claim 22, wherein the PCS layer is filled with graphene particles and contains 0.5% to 2% by weight of graphene.

24. A substrate comprising a coating applied to at least one surface by carrying out the method of claim 22.

25. An aircraft component comprising the substrate described in claim 24.

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