Adhesion promoters for composites and methods thereof

Abstract

The invention relates to an adhesion promoter for composite materials and a method thereof. The present application discloses an adhesion promoter composition comprising one or more reactive silanes, one or more swelling agents, and one or more organic solvents wherein the one or more reactive silanes and the one or more swelling agents form a complex. The one or more reactive silanes may include an amine functional group, an epoxy functional group, a mercapto functional group, an isocyanate functional group, or a combination thereof. The one or more swelling agents are selected from the group that may include phenol or naphthol derivatives. The present application also discloses a composite component comprising the adhesion promoter composition and a method of coating the adhesion promoter composition.

Description

Technical Field

[0001] The present teachings relate generally to adhesion promoters and, more particularly, to adhesion promoters for composite materials and methods of making the same. Background Art

[0002] Polyaryletherketone (PAEK) thermoplastic composites have a combination of properties that are desirable in a variety of applications in aerospace and other industries. These PAEK composites have poor compatibility with current qualified aerospace topcoats that were originally developed for metal and thermoset substrates. Topcoats, sealants and surface coatings play an important role in the successful assembly of various aircraft components and are widely used in manufacturing and maintenance.

[0003] Unfortunately, coatings, sealants and adhesives that provide acceptable adhesion to thermosets do not meet the same adhesion requirements when applied to polyaryletherketone (PAEK), polyetherketoneketone (PEKK), polyetheretherketone (PEEK) and other thermoplastics or thermoplastic composites after surface preparation by sanding. Although acceptable adhesion of these topcoats on thermoplastics can be achieved using surface preparation methods other than sanding, sanding is the most practical surface preparation technique in repair and rework scenarios.

[0004] There is interest in developing a chemical treatment that is effective and practical in achieving adequate adhesion, either alone or in combination with other surface preparation methods for aerospace composites, such as but not limited to sanding. Summary of the invention

[0005] A brief summary is provided below to provide a basic understanding of some aspects of one or more examples of the present teachings. This summary is not an extensive review, nor is it intended to identify the key or important elements of the present teachings, nor is it intended to delineate the scope of the present disclosure. Instead, its primary purpose is merely to present one or more concepts in a simplified form as a preface to a subsequent detailed description.

[0006] Disclosed is an adhesion promoter composition. The adhesion promoter composition includes one or more reactive silanes, one or more swelling agents and one or more organic solvents, wherein the one or more reactive silanes form a complex with the one or more swelling agents. Embodiments of the adhesion promoter composition include wherein the one or more reactive silanes form a complex with the one or more swelling agents through interaction (e.g., hydrogen bonds and / or ionic bonds). The molar ratio of the one or more reactive silanes to the one or more swelling agent functional groups is from about 0.1:1 to about 1.5:1. The one or more reactive silanes may include an amine functional group, an epoxy functional group, a thiol functional group, an isocyanate functional group or a combination thereof. The one or more reactive silanes may include a polyalkoxysilane. The one or more reactive silanes may include bis-trimethoxysilane, bis-triethoxysilane, tris-trimethoxysilane, tris-triethoxysilane or a combination thereof. The one or more reactive silanes are selected from the group consisting of 3-aminopropyltrimethoxysilane (APTMS), 3-aminopropyltriethoxysilane (APTES), 3-aminopropylmethyldimethoxysilane (APMDMS), 3-aminopropylmethyldiethoxysilane (APMDES), 3-aminopropyldimethylethoxysilane (APDMES), 3-(2-aminoethylamino)propyltrimethoxysilane (AEPTMS), 3-(2-aminoethylamino)propyltriethoxysilane (EEPTTES), 3-(2-aminoethylamino)propyldimethoxymethylsilane (AEDMMS), 3-(2-aminoethylamino)propyldiethoxymethylsilane (EEDMMES), 3-[2-(2-aminoethylamino)ethylamino]propyltrimethoxysilane (TMSDETA) and 3-[2-(2-aminoethylamino)ethylamino]propyltriethoxysilane (TESDETA). The one or more reactive silanes are selected from the group which may include bis[3-(trimethoxysilyl)propyl]amine (BTMSPA), 1,2-bis(trimethoxysilyl)ethane (BTMSE), 1,8-bis(trimethoxysilyl)octane (BTMSO), tris[3-(trimethoxysilyl)propyl]isocyanurate (TMSIC), 1,2-bis(triethoxysilyl)ethane (BTESE), 1,8-bis(triethoxysilyl)octane (BTESO) and bis[3-(triethoxysilyl)propyl]tetrasulfide (BTSTS).Other functional silanes may include (3-glycidyloxypropyl) trimethoxysilane (GPTMS), (3-glycidyloxypropyl) triethoxysilane (GPTES), [2-(3,4-epoxycyclohexyl) ethyl] trimethoxysilane (ECTMS), [2-(3,4-epoxycyclohexyl) ethyl] triethoxysilane (ECTES), (3-mercaptopropyl) trimethoxysilane (MPTMS), (3-mercaptopropyl) triethoxysilane (MPTES), 3-(trimethoxysilyl) propyl isocyanate (TMSPI) and 3-(triethoxysilyl) propyl isocyanate (TESPI) or a combination thereof. The one or more reactive silanes are present in the adhesion promoter composition in an amount of 1 wt % to 10 wt %, based on the total weight of the adhesion promoter composition. The one or more swelling agents are present in the adhesion promoter composition in an amount of 1 wt % to 10 wt %, based on the total weight of the adhesion promoter composition. The one or more swelling agents are selected from the group consisting of phenol or naphthol derivatives, in particular chlorine-substituted phenol or naphthol derivatives, such as 2-chlorophenol (2CPO), 3-chlorophenol (3CPO), 4-chlorophenol (CPhO), 2-amino-4-chlorophenol (ACPO), 2-allyl-4-chlorophenol (AlCPO), 2-benzyl-4-chlorophenol (BCPO), 2-methoxy-4-chlorophenol (MCPO), 4-chloro-1-naphthol (CPO), NO), 2-chloro-1-naphthol (2CNO), 1-chloro-2-naphthol (C2NO), 2,4-dichloro-1-naphthol (DCNO), 2-allyl-4-chloro-1-naphthol (ACNO), 3,3'-dichloro-[1,1'-binaphthyl]-2,2'-diol, 2,2'-methylenebis(4-chlorophenol) (BCPhO), 4,4'-isopropylidenebis(o-chlorophenol), and 2,6-bis(2-hydroxy-5-chlorobenzyl)-4-chlorophenol. The one or more organic solvents may include alcohols, ethers, esters, ketones, such as isopropyl alcohol, butanol, di(propylene glycol) monomethyl ether (DPM), dipropylene glycol dimethyl ether (DMM), propylene glycol monopropyl ether (PnP), dimethyl isosorbide, propylene glycol monomethyl ether acetate (MPA), butyl acetate, amyl acetate, ethylene glycol diacetate, propylene glycol diacetate, methyl isobutyl ketone (MIBK), methyl amyl ketone (MAK), or a combination thereof.

[0007] A composite component is disclosed. The composite component includes a thermoplastic composite material, an adhesion promoter composition disposed on the surface of the thermoplastic composite material, the adhesion promoter composition may include one or more reactive silanes and one or more swelling agents, wherein the one or more reactive silanes form a composite with the one or more swelling agents. The composite component also includes a situation in which the adhesion promoter composition diffuses into at least a portion of the thermoplastic composite material. The composite component also includes a surface coating, which is disposed on the surface of the thermoplastic composite material where the adhesion promoter is disposed. An embodiment of the composite component may include wherein the one or more reactive silanes form a composite with the one or more swelling agents through interaction (e.g., hydrogen bonds and / or ionic bonds). The one or more reactive silanes may form a chemical reaction with the surface coating. The thermoplastic composite material may include polyaryletherketone (PAEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), polyetherimide (PEI), polyimide, or a combination thereof. The surface coating may include an epoxy polymer formulation, a polyurethane polymer formulation, a polythioether polymer formulation, or a combination thereof. The one or more reactive silanes are selected from the group consisting of 3-aminopropyldimethylethoxysilane (APDMES), 3-aminopropyltrimethoxysilane (APTMS), 3-aminopropyltriethoxysilane (APTES) and 3-aminopropylmethyldimethoxysilane (APMDMS). The one or more reactive silanes are selected from the group consisting of bis[3-(trimethoxysilyl)propyl]amine (BTMSPA), 1,2-bis(trimethoxysilyl)ethane (BTMSE), 1,8-bis(trimethoxysilyl)octane (BTMSO), tris[3-(trimethoxysilyl)propyl]isocyanurate (TMSIC), 1,2-bis(triethoxysilyl)ethane (BTESE), 1,8-bis(triethoxysilyl)octane (BTESO) and bis[3-(triethoxysilyl)propyl]tetrasulfide (BTSTS). Other functional silanes may include (3-glycidyloxypropyl)trimethoxysilane (GPTMS), (3-glycidyloxypropyl)triethoxysilane (GPTES), [2-(3,4-epoxycyclohexyl)ethyl]trimethoxysilane (ECTMS), [2-(3,4-epoxycyclohexyl)ethyl]triethoxysilane (ECTES), (3-mercaptopropyl)trimethoxysilane (MPTMS), (3-mercaptopropyl)triethoxysilane (MPTES), 3-(trimethoxysilyl)propyl isocyanate (TMSPI) and 3-(triethoxysilyl)propyl isocyanate (TESPI) or a combination thereof. The one or more swelling agents are selected from the group consisting of 4-chloro-1-naphthol (CNO), 4-chlorophenol (CPhO) and 2,2'-methylenebis(4-chlorophenol) (BCPhO).The one or more swelling agents are selected from the group consisting of phenol or naphthol derivatives, in particular chlorine-substituted phenol or naphthol derivatives, such as 2-chlorophenol (2CPO), 3-chlorophenol (3CPO), 4-chlorophenol (CPhO), 2-amino-4-chlorophenol (ACPO), 2-allyl-4-chlorophenol (AlCPO), 2-benzyl-4-chlorophenol (BCPO), 2-methoxy-4-chlorophenol (MCPO), 4-chloro-1-naphthol (CPO), NO), 2-chloro-1-naphthol (2CNO), 1-chloro-2-naphthol (C2NO), 2,4-dichloro-1-naphthol (DCNO), 2-allyl-4-chloro-1-naphthol (ACNO) and 3,3'-dichloro-[1,1'-binaphthyl]-2,2'-diol, 2,2'-methylenebis(4-chlorophenol) (BCPhO), 4,4'-isopropylidenebis(o-chlorophenol) and 2,6-bis(2-hydroxy-5-chlorobenzyl)-4-chlorophenol. The molar ratio of the one or more reactive silanes to the one or more swelling agents is from about 0.1:1 to about 1.5:1.

[0008] A method for applying an adhesion promoter composition is disclosed. The method for applying the adhesion promoter composition includes contacting a reactive silane compound, a swelling agent, and one or more organic solvents to prepare the adhesion promoter composition, wherein the organic solvent may include dipropylene glycol dimethyl ether (DMM), propylene glycol monopropyl ether (PnP), methyl isobutyl ketone (MIBK) or a combination thereof. The method also includes applying the adhesion promoter composition to the surface of a thermoplastic or a thermoplastic composite. The method also includes applying a surface coating on the adhesion promoter composition.

[0009] The method of applying the adhesion promoter composition may include thermally curing the adhesion promoter at a temperature of about 50° C. to about 200° C. for about 1 minute to about 120 minutes. The method of applying the adhesion promoter composition may include grinding the surface of the thermoplastic or thermoplastic composite before applying the adhesion promoter composition to the surface of the thermoplastic or thermoplastic composite.

[0010] The features, functions, and advantages discussed can be achieved independently in various embodiments or can be combined in yet other embodiments, and more details can be found in the following description. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] The accompanying drawings are incorporated in and constitute a part of this specification, and illustrate embodiments of the present teachings and, together with the description, serve to explain the principles of the present disclosure. In the drawings:

[0012] Figure 1 A schematic diagram of a vehicle of the present disclosure is shown.

[0013] Figure 2is a schematic diagram of the diffusion-interlocking surface treatment method of the present disclosure.

[0014] Figure 3 is a flow chart illustrating a method of applying an adhesion promoter composition of the present disclosure.

[0015] Figure 4 are images of coated and treated SIJA bonded panels after bond testing.

[0016] It should be noted that some details of the drawings have been simplified and are drawn to facilitate understanding of the present teachings without maintaining strict structural accuracy, detail, and scale. DETAILED DESCRIPTION

[0017] Reference will now be made in detail to illustrative examples of the present teachings, examples of which are illustrated in the accompanying drawings. Wherever possible, the same reference numerals will be used throughout the drawings to refer to the same, similar or like parts.

[0018] It would be advantageous to develop an adhesion promoting chemical treatment that provides effective and practical adhesion in achieving adequate adhesion in thermoplastic composites, either alone or in combination with other surface preparation methods for aerospace composites. The adhesion promoting method should be suitable for complex geometries, meet environmental health and safety standards, be compatible with surface preparation of composites for coating, sealant, adhesive or surface coating applications, and optionally be capable of being combined with physical surface preparation techniques (e.g., sanding or grinding) to be effective.

[0019] Other requirements for adhesion promoters or adhesion promoter compositions for such applications include meeting adhesion requirements, minimizing or eliminating the following issues: adverse effects on the cure of subsequent topcoats, risk of structural damage to the composite material, and added weight. In addition, the adhesion promoter composition should have stability, a pot life of at least 4 hours, an adequate overcoating window for manual application of subsequent topcoats, and convenient, simple application.

[0020] The present disclosure provides a kind of adhesion promoter composition, it comprises one or more reactive silanes, one or more swelling agents and one or more organic solvents, wherein, the one or more reactive silanes form a composite with the one or more swelling agents.In an embodiment, the composite part including thermoplastics or thermoplastic composites can be incorporated with one or more adhesion promoter compositions as described herein.In such composite materials, by coating the adhesion promoter composition, the adhesion promoter composition diffuses into at least a portion of the thermoplastics or thermoplastic composites, so that it is possible to improve the adhesion of the surface coating deposited on one or more surfaces of the thermoplastics or thermoplastic composites on which the adhesion promoter has been deposited.The present disclosure also provides a method for applying the adhesion promoter composition, which includes contacting a reactive silane compound containing an amine functional group, a swelling agent and one or more organic solvents (including dipropylene glycol dimethyl ether (DMM), propylene glycol monopropyl ether (PnP), methyl isobutyl ketone (MIBK) or a combination thereof) to prepare the adhesion promoter composition, applying the adhesion promoter composition to the surface of the thermoplastic composite by one or more automatic or manual coating techniques, and applying a surface coating on the adhesion promoter composition.

[0021] The following description of various exemplary aspects is merely exemplary in nature and is in no way intended to limit the present disclosure, its application, or uses.

[0022] As used throughout, ranges are used as shorthand for describing each value within a range. Any value within the range can be selected as the endpoint of the range. In addition, all references cited herein are incorporated herein by reference in their entirety. In the event that the definition of the present disclosure conflicts with the definition of the cited reference, the present disclosure shall prevail.

[0023] Unless otherwise indicated, all percentages and amounts expressed herein and elsewhere in the specification are to be understood as referring to percentages by weight. The amounts given are based on the active weight of the material.

[0024] As used herein, "free" or "substantially free" of a material can refer to a composition, component, or phase in which the material is present in an amount less than 10.0 weight percent, less than 5.0 weight percent, less than 3.0 weight percent, less than 1.0 weight percent, less than 0.1 weight percent, less than 0.05 weight percent, less than 0.01 weight percent, less than 0.005 weight percent, or less than 0.0001 weight percent, based on the total weight of the composition, component, or phase.

[0025] In addition, all numerical values ​​are "about" or "approximately" the values ​​shown, and experimental errors and fluctuations expected by a person of ordinary skill in the art are taken into account. It should be understood that all numerical values ​​and ranges disclosed herein are approximate values ​​and ranges. The terms "about" or "approximately" and "substantially" or "approximately" with respect to an amount or measurement value mean that the feature, parameter or value does not need to be precisely achieved. On the contrary, deviations or variations, including, for example, tolerances, measurement errors, measurement accuracy limitations, and other factors known to those skilled in the art, may occur in amounts that do not exclude the effect that the feature is intended to provide. As used herein, "about" means within ±5% of the target value, maximum value, or minimum value.

[0026] All references cited herein are hereby incorporated by reference in their entirety. In the event of a conflict in a definition in the present disclosure and that of a cited reference, the present disclosure controls.

[0027] The present disclosure provides one or more adhesion promoter compositions. As used herein, the term "adhesion promoter" refers to a class of materials consisting of liquid reactive silanes and other additives in an organic solvent. The adhesion promoter compositions disclosed herein include one or more optional swelling agents, which can or are configured to improve the conventional methods for preparing surfaces for processing or applying coatings, coatings or sealants. For example, as further described herein, the adhesion promoter compositions disclosed herein can or are configured to synchronously or simultaneously penetrate and / or swell one or more top layers of a surface, and provide chemical or physical interlocking components with one or more ingredients in a surface and adhesion promoter composition. Compared with currently known adhesives or adhesion promoters known in the art, the adhesion promoter compositions disclosed herein can also or are configured to provide improved adhesion of surface coatings such as adhesives or sealants to composite materials.

[0028] The present disclosure provides bonding compositions and coating methods for compositions that provide suitable adhesion to complex geometries, meet various regulatory approvals related to environmental health and safety, inherent removal of residual mold release agents or other factory contaminants from composite part surfaces. In addition, if necessary, the adhesion promoters of the present teachings are suitable for combination with physical surface preparation techniques, such as solvent wiping with isopropyl alcohol or other cleaning solvents, sandblasting, cleaning with sandpaper or mild abrasives (e.g., Scotch-Brite TM ) sanding or grinding, thereby being effective. Other features of the present disclosure include adhesion promoter compositions that have no adverse effect on the cure of subsequent topcoats, pose no risk of structural damage to any composite material, add minimal weight, are stable, have adequate pot life, and have a short minimum overcoating time at ambient temperature.

[0029] Figure 1A schematic diagram of a vehicle 100 according to one embodiment is shown. As shown, the vehicle 100 may include an airplane. The vehicle 100 may also or alternatively include other types of aircraft, such as a helicopter, an unmanned aerial vehicle (UAV), a spacecraft, etc. In other embodiments, the vehicle 100 may be or include a car, a boat, a train, etc. In other embodiments, the systems and methods described below may not be implemented in a vehicle, but may be implemented in a building.

[0030] The vehicle 100 may include one or more lavatories (one is shown: 110). The lavatory 110 may include a sink 112, a toilet 114, and a sensor 116. The sensor 116 may sense / determine whether the lavatory 110 is occupied (e.g., occupied by a passenger) or unoccupied. For example, the sensor 116 may be or include a motion sensor. The vehicle 100 may also include one or more galleys or onboard galleys (one is shown: 120). The galley 120 may include a sink 122, a dishwasher 124, and an ice maker 126. A composite material or a method of applying the composite material comprising an adhesion promoter composition described herein integrated on or in one or more inner or outer surfaces or components 128, 130, 132 of the vehicle 100 may be applied to improve the adhesion between the composite layers or coatings thereon. The one or more components 128, 130, 132 may include, for example, an adhesion promoter composition for coating one or more layers or improving the adhesion between the composite material and one or more applied coatings or sealants.

[0031] The example of the polymer material that can be used (for example, as substrate) for surface coating with adhesion promoter composition of the present disclosure and / or subsequent surface coating includes the polymer material that serves as matrix with one or more fiber combinations. In an example, the material that can be used for the practice of the present disclosure includes fiber reinforced plastic (FRP), which includes the polymer material combined with inorganic fiber (for example carbon fiber, carbon nanotube, graphite, glass fiber, glass, metal, metal alloy or metallized fiber and metal coated glass fiber, alumina fiber or boron fiber). In an example, fiber reinforced plastic can include organic fiber, for example nylon fiber or aramid fiber. In an example, fiber reinforced plastic can include organic fiber and / or inorganic fiber that are mixed into thermosetting or epoxy resin.

[0032] In one example, carbon fiber reinforced plastic (CFRP) or glass fiber reinforced plastic (GFRP), which are polymeric articles made therefrom, are imparted with improved interlaminar adhesion by using or applying an adhesion promoter composition suitable for use in aircraft structures, etc. However, the present disclosure is not limited to these types of materials, and articles formed from other polymers may also be used in the presently disclosed methods of the present disclosure.

[0033] Components, parts or composite components (such as carbon fiber reinforced polymer (CFRP) components) are initially laid up in multiple layers, collectively referred to as "preforms". As used herein, the term "uncured composite component" or "preform" refers to one or more layers of composite material impregnated with uncured or in some cases partially cured resin. For example, the uncured composite component can be a fiber-reinforced uncured thermosetting polymer composite component. The individual fibers in each layer of the preform can be arranged parallel to each other, but different layers can show different fiber orientations to increase the strength of the resulting composite component along different dimensions. The preform may include a viscous resin that is cured to harden the preform into a composite component (for example, for use in an aircraft). Carbon fiber layers that have been impregnated with uncured thermosetting resins or thermoplastic resins are called "prepregs". As used herein, the term "prepreg" refers to a stack of pre-impregnated composite plies, such as epoxy resin-impregnated unidirectional composite tapes, woven plies or short slices thereof. The prepreg can be flexible before curing, and is usually cured by heat and pressure curing or curing in an autoclave. Other types of carbon fiber include "dry fibers" that are not impregnated with thermosetting resins but may contain tackifiers or binders. Dry fibers may be infused with resin prior to curing. For thermosetting resins, hardening is a one-way process called curing, while for thermoplastic resins, the resin can return to a remodelable or viscous form if reheated.

[0034] With respect to fiber-reinforced thermosetting polymer composite parts, curing generally refers to the application of heat and / or pressure to crosslink and consolidate the fibers in the fiber-reinforced thermosetting polymer composite part. Although thermosetting resins can be partially cured (i.e., crosslinked) without the application of pressure, this generally results in poor consolidation of the part. Therefore, as used herein, the term "curing" includes applying heat (to cure / crosslink) and applying pressure (to consolidate) to a fiber-reinforced thermosetting polymer composite part, such as the thermosetting composite part of the present disclosure.

[0035] In some embodiments, the composite component is cured by applying heat and / or pressure to the composite component. Heat and / or pressure can be applied according to a predetermined curing schedule that specifies the applied pressure, temperature, and the duration of the pressure and / or temperature. In some embodiments, the composite component is cured only by pressure. For example, the composite component can be cured by applying pressure at room temperature. The pressure can be positive or negative pressure. The adhesion promoter composition can be used for manufacturing or processing such composite components on one or more surfaces or between layers, to at least improve the adhesion between layers or improve the adhesion of surface coatings on composite materials or parts. Although composite materials comprising thermosetting resins are suitable for the adhesive formulations described in the present disclosure, they can also be applied to thermoplastic materials.

[0036] Figure 2is a schematic diagram of an adhesion promoter technology described in the present disclosure, called the diffusion-interlocking surface treatment method. The diffusion-interlocking surface treatment is a concept based on the swelling of a thin surface layer of a polymer, followed by subsequent interaction of reactive silanes or other cross-linkable chemicals, which can form an interfacial cross-linking network and enhance the adhesion layer. These interfacial cross-linking networks can be produced by forming a composite between one or more reactive silanes or other cross-linkable chemicals and one or more swelling agents via interactions such as hydrogen bonding and / or covalent bonding. The diffusion-interlocking method is based on the chemical inertness of the polymer backbone of PAEK, other thermoplastic or thermoset composites, and the need to enhance adhesion by chemical and physical means using common methods. Examples of the diffusion-interlocking method are shown in Figure 2 Described in. The proposed mechanism 200 involves three stages. First, the diffusion of the active component (in this case, aminosilane 202, APS in this example) and the swelling agent 204 causes the surface and the surface layer to be penetrated by the adhesion promoter composition. This requires the partial swelling of the surface of the active component to penetrate the sublayer. Next, the active component causes the formation of a composite 208 to provide interlocking and enhanced adhesion by crosslinking 206 of sol-gel hydrolysis and condensation reaction or other crosslinking mechanisms (such as covalent bonds or hydrogen bonds). Finally, the active layer provides a strong combination with a coating, a sealant or other surface finish by the reaction 210 or interaction between the functional groups of the activator and the reactive chemicals of the surface finish or by molecular entanglement / network. In an example, the adhesion promoter can form an interpenetrating polymer network (IPN) or interpenetrate with a composite surface in the adhesion promoter composition by means of its components. An interpenetrating polymer network (IPN) can refer to a polymer or polymer layer comprising at least two polymer networks that react at least partially with each other. In the adhesion promoters of the present teachings, the reactive silane and the swelling agent interact and form an IPN by hydrolysis and condensation. In the example including amine functional groups, the amine groups can also react with primers that can be applied after the adhesion promoter composition. The two or more networks can be considered to be physically entangled, and in some cases chemically entangled, but generally irreversible. Figure 2 In the example given in , the swelling agent is 4-chloronaphthol (CNO), which is a known good solvent for PEEK and other PAEKs. The active ingredient is 3-aminopropyltriethoxysilane (APS). The aminosilane 202 and the swelling agent 204 can form hydrogen bonds or ionic bonds because CNO is a weak acid and the aminosilane is a weak base, which causes network formation and prevents volatilization of the CNO or silane. After exposure to atmospheric moisture (or by pre-dosing the silane with water), the silane undergoes hydrolysis 210 and condensation to form a sol-gel-like coating 212. The active ingredient is typically less than about 5% in the mixed solvent solution, forming a very thin film on the composite surface.

[0037] The one or more adhesion promoters may include, but are not limited to, one or more compounds (including at least one or more reactive silanes), at least one or more swelling agents, and one or more organic solvents, wherein the one or more reactive silanes form a complex with the one or more swelling agents. Organosilanes or reactive silanes are generally understood to be, but not necessarily limited to, multifunctional silicon-containing molecules comprising reactive functional groups and one or more hydrolyzable alkoxy groups. Exemplary silanes may include, but are not limited to, amine-functional silanes, epoxy-functional silanes, mercapto-functional silanes, isocyanurate-functional silanes, polyalkoxy-functional silanes, or combinations thereof. In addition, exemplary silanes may include: trialkoxysilanes, such as trimethoxy, triethoxy, tripropoxysilane; dialkoxysilanes, such as dimethoxy, diethoxy, dipropoxysilane; monoalkoxysilanes, such as dimethylmethoxy, dimethylethoxy, diethylmethoxy, diethylethoxysilane; or combinations thereof.

[0038] Exemplary amine functional silanes can include, but are not limited to, 3-aminopropyltrimethoxysilane (APTMS), 3-aminopropyltriethoxysilane (APTES), 3-aminopropylmethyldimethoxysilane (APMDMS), 3-aminopropylmethyldiethoxysilane (APMDES), 3-aminopropyldimethylethoxysilane (APDMES), 3-(2-aminoethylamino)propyltrimethoxysilane (AEPTMS), 3-(2-aminoethylamino) ... Silane (AEPTES), 3-(2-aminoethylamino)propyl dimethoxymethylsilane (AEDMMS), 3-(2-aminoethylamino)propyl diethoxymethylsilane (AEDMES), 3-[2-(2-aminoethylamino)ethylamino]propyl trimethoxysilane (TMSDETA), 3-[2-(2-aminoethylamino)ethylamino]propyl triethoxysilane (TESDETA), 3-aminopropyl tris(2-(2-methoxyethoxy)ethoxy ) silane, 3-aminopropyl triisopropenyloxysilane, 3-aminopropyl tri(butyl ketone oxide) silane, 4-aminobutyl triethoxysilane, N-2-(aminoethyl)-3-aminopropyl tri(2-ethylhexyloxy) silane, 3-aminopropyl dimethylethoxysilane, 3-aminopropyl diisopropylethoxysilane, p-aminophenyl trimethoxysilane, m-aminophenyl trimethoxysilane, 3-aminopropyl phenyl diethoxysilane, and cyclic azasilanes such as 2,2-dimethoxy-1 ,6-diaza-2-silacyclooctane, 2,2-dimethoxy-N-n-butyl-1-aza-2-silacyclopentane, 2,2-diethoxy-1-aza-2-silacyclopentane, 2,2-dimethoxy-N-tert-butyl-1-aza-2-silacyclopentane, 2,2-dimethoxy-N-methyl-1-aza-2-silacyclopentane, 2,2-dimethoxy-N-allyl-1-aza-2-silacyclopentane, 3-aminopropyltriethoxysilane and 3-aminopropyltrimethoxysilane or a combination thereof.

[0039] Exemplary glycidoxy-functional or epoxy-functional silanes can include, but are not limited to, glycidoxypropyltrialkoxysilanes (e.g., glycidoxypropyltrimethoxysilane, (3-glycidoxypropyl)trimethoxysilane (GPTMS), (3-glycidoxypropyl)triethoxysilane (GPTES), etc.), 3-(2,3-glycidoxypropyl)methyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-(2,3-glycidoxypropyl)methyldimethoxysilane, [2-(3,4-epoxycyclohexyl)ethyl]trimethoxysilane (ECTMS), 2-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, 8-glycidoxyoctyltrimethoxysilane, 1-(3-glycidoxypropyl)-1,1,3,3,3-pentaethoxy-1,3-disilpropane, or combinations thereof.

[0040] Exemplary mercapto-functional silanes may include, but are not limited to, (3-mercaptopropyl)trimethoxysilane (MPTMS), (3-mercaptopropyl)triethoxysilane (MPTES), 11-mercaptoundecyltrimethoxysilane, s-(octanoyl)mercaptopropyltriethoxysilane, (mercaptomethyl)methyldiethoxysilane, 3-mercaptopropylmethyldimethoxysilane, mercaptopropyltrialkoxysilanes (e.g., mercaptopropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane), mercaptoundecyltrimethoxysilane, (mercaptomethyl)methyldiethoxysilane, or combinations thereof.

[0041] Exemplary isocyanurate functional silanes may include, but are not limited to, tris(trimethoxysilylpropyl)isocyanurate, tris(triethoxysilylpropyl)isocyanurate, tris[3-(trimethoxysilyl)propyl]isocyanurate (TMSIC), etc. Exemplary isocyanate functional silanes include, but are not limited to, 3-(trimethoxysilyl)propyl isocyanate (TMSPI) and 3-(triethoxysilyl)propyl isocyanate (TESPI), (isocyanatomethyl)methyldimethoxysilane, 3-isocyanatopropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, isocyanatopropylmethyldimethoxysilane, 3-isocyanatopropylmethyldiethoxysilane, isocyanatomethyltrimethoxysilane, isocyanatomethyltrimethoxysilane, or combinations thereof.

[0042] Exemplary multi-alkoxy functional silanes may include, but are not limited to, bis-trimethoxysilane, bis-triethoxysilane, tris-trimethoxysilane, tris-triethoxysilane, or combinations thereof. Examples also include, but are not limited to, bis[3-(trimethoxysilyl)propyl]amine (BTMSPA), 1,2-bis(trimethoxysilyl)ethane (BTMSE), 1,8-bis(trimethoxysilyl)octane (BTMSO), tris[3-(trimethoxysilyl)propyl]isocyanurate (TMSIC), 1,2-bis(triethoxysilyl)ethane (BTESE), 1,8-bis(triethoxysilyl)octane (BTESO), and bis[3-(triethoxysilyl)propyl]tetrasulfide (BTSTS), or combinations thereof.

[0043] Other exemplary silanes can include, but are not limited to, bis(trimethoxysilylethyl)benzene, bis(triethoxysilylethyl)benzene, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, vinyltrimethoxysilane, allyltrimethoxysilane, or combinations thereof.

[0044] In examples of adhesion promoter compositions that include more than one reactive silane in the composition, it may be advantageous for the first reactive silane to be different from the second reactive silane so that additional organic functional groups can be added to the adhesion promoter composition, thereby providing additional potential reactive functional groups present in the adhesion promoter composition. Without being bound by any particular theory, the additional functional group chemistry in the adhesion promoter composition may provide versatility or utility for use in numerous applications of swelling agents, polymer composites, substrates, surface coatings, or combinations thereof.

[0045] Based on the gross weight of the adhesion promoter composition, the one or more reactive silanes may be present in an amount of about 0.01 wt % to about 10 wt %. For example, based on the gross weight of the adhesion promoter composition, the one or more reactive silanes may be present in an amount of about 0.1 wt %, about 0.5 wt %, about 1 wt %, about 1.5 wt %, about 2 wt %, about 3 wt %, about 4 wt %, or about 5 wt % to about 6 wt %, about 6.5 wt %, about 7 wt %, about 8 wt %, about 9 wt %, or about 10 wt %. In another example, the one or more reactive silanes may be present in an amount of about 0.1 wt % to about 10 wt %, about 2 wt % to about 8 wt %, or about 4 wt % to about 6 wt %.

[0046] The swelling agent of the present teaching provides at least partial swelling of the surface or subsurface as at least one or more active ingredients and is added to the adhesion promoter to penetrate the layer or sublayer. The swelling agent also includes functional groups that can interlock or crosslink to form a complex through sol-gel or other crosslinking mechanisms (e.g., covalent bonds or hydrogen bonds) to provide interlocking and enhanced adhesion when using the adhesion promoter composition described herein.

[0047] Illustrative examples of swelling agents for use in the adhesion promoter composition of the present disclosure include, but are not limited to, 4-chloro-1-naphthol (CNO), 4-chlorophenol (CPhO), and 2,2'-methylenebis(4-chlorophenol) (BCPhO), or combinations thereof. Other examples of swelling agents may include, but are not limited to, phenol or naphthol derivatives, chlorine-substituted phenols or naphthol derivatives, such as 2-chlorophenol (2CPO), 3-chlorophenol (3CPO), 4-chlorophenol (CPhO), 2-amino-4-chlorophenol (ACPO), 2-allyl-4-chlorophenol (AlCPO), 2-benzyl-4-chlorophenol (BCPO), 2-methoxy-4-chlorophenol (MCPO), 4-chloro-1-naphthol (CNO), 2- Chloro-1-naphthol (2CNO), 1-chloro-2-naphthol (C2NO), 2,4-dichloro-1-naphthol (DCNO), 2-allyl-4-chloro-1-naphthol (ACNO) and 3,3'-dichloro-[1,1'-binaphthyl]-2,2'-diol, 2,2'-methylenebis(4-chlorophenol) (BCPhO), 4,4'-isopropylidenebis(o-chlorophenol), 2,6-bis(2-hydroxy-5-chlorobenzyl)-4-chlorophenol, or a combination thereof.

[0048] Based on the gross weight of the adhesion promoter composition, the one or more swelling agents may be present in an amount of about 0.01 wt % to about 10 wt %. For example, based on the gross weight of the adhesion promoter composition, the one or more swelling agents may be present in an amount of about 0.1 wt %, about 0.5 wt %, about 1 wt %, about 1.5 wt %, about 2 wt %, about 3 wt %, about 4 wt % or about 5 wt % to about 6 wt %, about 6.5 wt %, about 7 wt %, about 8 wt %, about 9 wt % or about 10 wt %. In another example, the one or more swelling agents may be present in an amount of about 0.1 wt % to about 10 wt %, about 2 wt % to about 8 wt % or about 4 wt % to about 6 wt %.

[0049] In certain descriptions of the composition of the adhesion promoter composition of the present disclosure, a molar ratio of silane to swelling agent may be used. The molar ratio of silane to swelling agent may be expressed as silane:swelling agent or silane / swelling agent, or as a fraction. In an example, silane:swelling agent is from about 0.1 to about 2.0, or from about 0.1:1 to about 2:1.

[0050] One or more organic solvents of the adhesion promoter composition can or be configured to disperse, dissolve, solvate or otherwise dissolve one or more substances or components of the adhesion promoter composition. One or more organic solvents of the adhesion promoter composition can also or be configured to disperse, dissolve, solvate or otherwise dissolve one or more substances, such as fat, oil or debris, on the surface in contact with the adhesion promoter composition. For example, one or more organic solvents of the adhesion promoter composition can or be configured to dissolve one or more reactive silanes, one or more swelling agents, any other functional additives or combinations thereof. One or more organic solvents can also or be configured to prepare for subsequent treatment or the surface of coating. For example, one or more organic solvents can or be configured to provide cleaning treatment or enhance the swelling characteristics of swelling agents at least in part when contacting the surface or substrate to be treated with coating. It should be understood that any organic solvents that can or be configured to dissolve one or more components of the adhesion promoter composition and / or prepare for subsequent treatment or apply surface treatment or coating can be used.

[0051] The one or more organic solvents may be or include, but are not limited to, aliphatic hydrocarbons, aromatic compounds (eg, aromatic hydrocarbons), halogenated hydrocarbons, nitrated hydrocarbons, ketones, amines, esters, alcohols, aldehydes, ethers, etc., or combinations thereof.

[0052] Exemplary aliphatic hydrocarbons that may be used as the one or more organic solvents may be or include, but are not limited to, n-pentane, n-hexane, n-heptane, n-octane, n-nonane, n-decane, white spirit, petroleum ether having a boiling range of 40-60° C. or 60-80° C. or 100-130° C., Isopar C, Isopar E, Isopar G, Isopar H, Isopar J and Isopar K or homologues thereof, 2,2,4-trimethylpentane, etc., cyclohexane, turpentine, limonene, or any combination thereof.

[0053] Exemplary aromatic compounds that may be used as the one or more organic solvents may be or include, but are not limited to, benzene, toluene, ethylbenzene, xylene, tetralin, hexafluoroxylene, etc., Solvesso 100, Solvesso 100S, Solvesso 150, Solvesso 150ND, 4-chlorotrifluorotoluene, etc., or any combination thereof.

[0054] Exemplary halogenated hydrocarbons that may be used as the one or more organic solvents may be or include, but are not limited to, carbon tetrachloride, chloroform, dichloroethane, trichloroethylene, tetrachloroethylene, dichloromethane, and the like, or combinations thereof.

[0055] Exemplary ketone organic solvents may be or include, but are not limited to, acetone, methyl ethyl ketone (MEK), diethyl ketone, methyl propyl ketone (MPK), dipropyl ketone, methyl isopropyl ketone, isophorone, methyl isobutyl ketone (MIBK), cyclopentanone, cyclohexanone, methyl amyl ketone (MAK), diisobutyl ketone, acetophenone, and the like, or combinations thereof.

[0056] Exemplary esters that can be used as the one or more organic solvents can be or include, but are not limited to, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, tert-butyl acetate, amyl acetate, isoamyl acetate, cellosolve acetate, γ-valerolactone, ethyl lactate, butyl lactate, dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, ethyl butyrate, and the like, or combinations thereof.

[0057] Exemplary alcohols that may be used as the one or more organic solvents may be or include, but are not limited to, methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, n-butanol, n-pentanol, isopentanol, cyclohexanol, n-octanol, ethylene glycol, diethylene glycol, 1,2-propylene glycol, and the like, or combinations thereof.

[0058] Exemplary ethers that can be used as the one or more organic solvents can be or include, but are not limited to, diethyl ether, diisopropyl ether, dibutyl ether, methyl tert-butyl ether, 1,4-dioxane, tetrahydrofuran, cyclopentyl methyl ether, 2-methyltetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol propyl ether, ethylene glycol monobutyl ether, diethylene glycol butyl ether, di(propylene glycol) monomethyl ether (DPM), dipropylene glycol dimethyl ether (DMM), propylene glycol monomethyl ether, propylene glycol monopropyl ether (PnP), propylene glycol butyl ether, dimethyl isosorbide, propylene glycol monomethyl ether acetate (MPA), ethylene glycol methyl ether acetate, ethylene glycol ethyl ether acetate, ethylene glycol diacetate, propylene glycol diacetate, oligomers of perfluoropolyethers (e.g. line, which is commercially available from Solvay in Houston, Texas, USA), etc., or a combination thereof.

[0059] Based on the gross weight of the adhesion promoter composition, the amount of the one or more organic solvents present in the adhesion promoter composition can be about 75 wt % to about 99.5 wt %. For example, based on the gross weight of the adhesion promoter composition, the amount of the one or more organic solvents present in the adhesion promoter composition can be about 75 wt %, about 80 wt %, about 85 wt % or about 90 wt % to about 95 wt %, about 98 wt %, about 99 wt % or about 99.5 wt %. In another example, based on the gross weight of the adhesion promoter composition, the amount of the one or more organic solvents present in the adhesion promoter composition can be about 75 wt % to about 99.5 wt %, about 80 wt % to about 99 wt %, about 85 wt % to about 95 wt % or about 85 wt % to about 90 wt %. In another example of the adhesion promoter composition, based on the gross weight of the adhesion promoter composition, the amount of the solvent can be about 25 wt %, about 30 wt %, about 35 wt % or about 40 wt %. In another example, the solvent can be present in an amount of about 25 wt % to about 40 wt %, about 25 wt % to about 30 wt %, or about 30 wt % to about 40 wt %.

[0060] Provided is a method for preparing any one or more adhesion promoter compositions disclosed herein. The method may include combining, mixing, blending or otherwise contacting the one or more organic solvents, the one or more reactive silanes, the one or more swelling agents, any optional catalysts or optional functional additives to prepare a mixture. It should be understood that the order of mixing or contacting each component of the adhesion promoter composition may be at least partially determined by the selected specific components. The method may also include purging the mixture with nitrogen to remove dissolved oxygen or other contaminants.

[0061] The method may also include a mixing method, including but not limited to homogenizing the adhesion promoter composition by shearing and / or cutting in an industrial mixer, an immersion mixer, a centrifugal mixer, a stirring mechanism, a shaker, etc., or any combination thereof. The adhesion promoter composition may be mixed for about 5 seconds (sec), about 10 seconds, about 30 seconds, or about 1 minute to about 2 minutes, about 3 minutes, about 5 minutes, about 10 minutes, about 30 minutes, or more.

[0062] Figure 3300 is a flow chart showing a method for applying an adhesion promoter composition of the present disclosure. The method 300 for applying an adhesion promoter composition may include contacting a reactive silane compound containing an amine functional group, a swelling agent, and one or more organic solvents (including dipropylene glycol dimethyl ether (DMM), propylene glycol monopropyl ether (PnP), methyl isobutyl ketone (MIBK) or a combination thereof) to prepare an adhesion promoter composition 302, applying the adhesion promoter composition to the surface of a thermoplastic composite material 304, and applying a surface coating to the adhesion promoter composition 306. The surface coating may require a primer to be applied before applying a surface coating, coating or composition containing a polymer. The surface coating may include an epoxy polymer formulation, a polyurethane polymer formulation, a polythioether polymer formulation or a combination thereof. The method for applying an adhesion promoter composition may include wherein the thermoplastic component includes polyaryletherketone (PAEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), polyetherimide (PEI), polyimide or a combination thereof. Other examples of suitable materials or composite materials may include polyamides, polyimides, poly(amide-imides), polyetherimides (PEI), and other high melting point thermoplastics. The adhesion promoter composition in the method for applying the adhesion promoter composition may include the components or ingredients described herein. Applying the adhesion promoter composition to the surface of the thermoplastic composite material may also include coating the adhesion promoter composition on the surface of the thermoplastic composite material. In an example, the reactive silane forms a chemical reaction with the surface, primer, or surface coating. In addition to other known coating methods known to those skilled in the art, the coating method may also include spraying, brushing, dipping, rolling, wiping, or a combination thereof. In some examples, sandblasting or other surface preparation techniques may be used. The adhesion promoter composition may include: having the general formula ((RO) n -SiY) m -(CH2) x -A, wherein n = 2-3, m = 1-2, Y is absent (when n = 3) or is a C1-C6 alkyl, x = 1-8, A = none, NH z , SH or epoxy group, z=1-2, and R=C1-C6 alkyl; one or more swelling agents; and one or more organic solvents; wherein the one or more reactive silanes form a complex with the one or more swelling agents through hydrogen bonds and / or ionic bonds.

[0063] Additional steps of the method of applying the adhesion promoter composition may include heating or grinding the surface of the thermoplastic or thermoplastic composite, such as thermally curing the adhesion promoter at a temperature of about 50°C to about 200°C for about 1 minute to about 120 minutes, or grinding the surface of the thermoplastic composite before applying the adhesion promoter composition to the surface of the thermoplastic composite. The method of treating the surface with the adhesion promoter composition may include one or more heating methods. The heating method may include, but is not limited to, ambient heating or evaporation, convection heating, infrared radiation heating, induction heating, or a combination thereof. In an example, the method may include a step of pausing, waiting, staying, or flashing or releasing solvent from the composite treated with the adhesion promoter composition under ambient conditions before any heating step at an elevated temperature. This evaporation step may also be accomplished using a heat gun or infrared lamp or any heating method disclosed herein. In an embodiment, thermal curing may be performed at a temperature of 120°C for 30 minutes, or from about 1 minute to about 60 minutes, or from about 5 minutes to about 45 minutes, or from about 10 minutes to about 30 minutes. The heating temperature may be from about 50°C to about 200°C, or from about 70°C to about 175°C, or from about 80°C to about 150°C.

[0064] The surface or substrate for coating adhesion promoter may include but is not limited to aluminum, titanium, carbon fiber composite material, carbon fiber reinforced composite material, glass fiber composite material, thermoplastic, thermosetting plastic or its combination.For example, the surface can be the surface of bridge truss, support column, building, building, vehicle (for example atmospheric vehicle, aviation vehicle, unmanned vehicle, aircraft, spacecraft, satellite, rocket, missile etc.) or any part thereof.In illustrative example, the polymer formulation layer in the method for applying adhesion promoter composition may include epoxy polymer formulation, polyurethane polymer formulation, polythioether polymer formulation, polyaryletherketone (PAEK), for example polyetheretherketone (PEEK), polyetherketoneketone (PEKK) or its combination.Adhesion promoter composition can be inert storage, store at room temperature, be stored in cold storage, be stored in refrigerator or its combination.In some instances, adhesion promoter composition can be made to reach room temperature before mixing or using. In certain aspects, the substrate or surface can be prepared prior to applying the adhesion promoter with an optional degreasing solvent wipe, and can then be applied to the substrate by spray, brush, roller, wipe, wipe on / off, pour, or a combination thereof.

[0065] The method of applying the adhesion promoter composition can include separating one or more particles and / or relatively large adhesion promoter aggregates from the adhesion promoter composition after homogenization or mixing. For example, the method can include separating particles and / or relatively large adhesion promoter aggregates from the adhesion promoter composition by filtering. Filtering can include passing the adhesion promoter composition containing one or more particles (e.g., glass particles) and / or relatively large adhesion promoter aggregates through a filter having a pore size of less than about 1 mm, less than about 0.5 mm, less than about 0.25 mm, or less than about 0.1 mm.

[0066] The method of treating a surface with an adhesion promoter composition may include applying the adhesion promoter composition to the surface or contacting the surface. The adhesion promoter composition may be contacted with the surface via a brush, screen, roller, syringe, extrusion gun, spray gun, etc. or any combination thereof. The adhesion promoter composition may also be applied using a PUMA® available from PPG Industries, Inc. of Sylmar, California, USA. The adhesion promoter composition may be capable of or configured to eliminate one or more steps in a conventional method or process for preparing a surface for application of a sealant, surface treatment, surface coating, etc. For example, in a conventional method for preparing a surface for application of a sealant, adhesive, surface treatment, or surface coating, the surface is first treated with a solvent and subsequently treated with an adhesion promoter or an adhesion promoter film is formed.

[0067] Example

[0068] While exemplary embodiments of adhesion promoter compositions are described with respect to the accompanying tables, it should be noted that alternative compositions, ratios of ingredients, or specific ingredients as described in the present teachings may be used in the compositions and applications of the adhesion promoters described herein.

[0069] Material:Swelling solvents or compounds (including 4-chloro-1-naphthol (CNO), 4-chlorophenol (CPhO)) were purchased from Aldrich. 2,2'-Methylenebis(4-chlorophenol) (BCPhO) was purchased from TCI. Solvents (including propylene glycol monopropyl ether (PnP), dipropylene glycol dimethyl ether (DMM)) were from Aldrich. Methyl isobutyl ketone (MIBK) was purchased from Sydney Solvent (commercial grade, 20L), and isopropanol was purchased from Merck. Silanes (including 3-aminopropyltriethoxysilane (APS), 3-aminopropyltrimethoxysilane (APTMS), 3-aminopropylmethyldimethoxysilane (APMDMS)) were all products of Aldrich. PAEK composites include carbon fiber reinforced PEEK, glass fiber reinforced PEKK or carbon fiber reinforced PEKK. The organic solvent primer, BMS10-103Gr A, 45GY005 chrome-free water-reducible epoxy primer, and BMS10-60 Desothane topcoat (CA8000 / B70846 / CA8000B) were purchased from PPG.

[0070] Preparation of diffusion-interlocking solution (taking 3.5% APMDES / BCPhO=0.375 solution as an example) :Generally, the solution is prepared in three steps. Step 1 includes preparing a mixed solvent, which in this embodiment is 50% MIBK, 20% DMM and 30% PnP. 500g MIBK, 300g PnP and 200g DMM are weighed into a 1.5L bottle. The mixture is magnetically stirred at 250rpm for 5 minutes to form a transparent clear solution. Step 2 includes preparing a BCPhO solution. 23g BCPhO is added to a covered 1.5L Schott bottle, followed by 965g of the mixed solvent. The mixture is magnetically stirred at 250rpm for 5 minutes to obtain a transparent yellow solution. Step 3 includes preparing an adhesion promoter spray solution (AP). 12g APMDES is added to the solution in step 2. The solution is magnetically stirred at 250rpm for 10 minutes. After standing at room temperature for 1 hour, the solution can be sprayed / coated. The preparation process is intended for exemplary purposes and may include alternative or supplementary methods or materials as disclosed in this teaching.

[0071] Application of Adhesion Promoter Diffusion-Interlocking Solution : Sanded or unsanded BMS8-422, BMS8-429 or BMS8-399 composites were cleaned by wiping with IPA multiple times. The solution was sprayed onto the sample using a high volume low pressure (HVLP) spray. The coating was allowed to dry in air for 30 minutes and then heated at 120°C for 30 minutes.

[0072] Preparation of sealant and bonding samples: Composite samples of 25 mm x 100 mm were cut from composite plates supplied by Boeing using a diamond saw. Cotton fabric or coated fiberglass mesh was used as the peeling medium. One end of the composite specimen was covered with 18 mm wide 3M Scotch tape to facilitate the creation of a debonding area at the composite surface for peel testing. The freshly prepared sealant was applied to the PEEK composite surface and the peeling medium (both surfaces) and care was taken to ensure complete wetting of the sealant on the test area. The peeling medium and the composite specimen were then placed in a sample holder made in-house and clamped with a metal clamp. Excess sealant was squeezed out of the running channel to obtain a 3.1 mm sealant thickness between the composite and the peeling medium. The two-part sealant was mixed just before coating according to the manufacturer's instructions. The assembly was cured for 14 days at room temperature.

[0073] Preparation of coated and bonded samples : The composite panels were cleaned with IPA and wiped with AC12165 DuPontAerospace wipe BMS15-5F before and after sanding. Sanding was performed with Flexovit 180 grit aluminum oxide sandpaper using a combination of air orbital and hand sanding for approximately 1 minute to obtain an even de-gloss finish. Sandpaper was changed after each sanding of 2 samples. The spraying was performed using a MACH 1A HVLP automatic spray gun with a fluid nozzle and a 94P cap. The inlet pressure was set to 40 PSI. In the coatings conforming to Configuration I, only the primer was used as the coating stack as shown in Table 1. As shown in Configuration II of Table 1, the primer and topcoat were used after the surface preparation of the remaining samples.

[0074] Table 1: Exemplary coatings on PEEK thermoplastic composites

[0075]

[0076] As shown in Table 1, two cross-coats of BMS10-103 Gr A primer were applied to the composite panels to obtain a film thickness of about 0.5 to about 0.8 mil. Before topcoating, the panels were dried at ambient for about 2 to about 2.5 hours. The topcoat was thoroughly mixed before coating. Before testing, BMS10-60 Desothane topcoat (CA8000 / B70846 / CA8000B) was sprayed onto the composite panels to obtain a film thickness of 2 to 3 mils and cured for 14 days at 24±5°C and 30%-60% RH. For the primer-only coating (Configuration I), the primer thickness was almost twice the primer thickness used in Configuration II (primer + topcoat).

[0077] Peel strength test: Quantitative adhesion was evaluated using a peel strength adhesion evaluation based on ASTM D3330 and BSS 7257. The minimum adhesion required was a peel strength of 20 pounds per inch of width, and the adhesion failure mode was a minimum 95% cohesive failure. The adhesion value and failure mode were recorded for each sample. Adhesion was measured after the sealant was dried and cured for 14 days ("dry adhesion") and after 7 days of fluid immersion in jet fuel or 3% NaCl solution.

[0078] Scratching Adhesion : Score adhesion is typically performed per BOEING specification support standard BSS7225. Score the test sample with a sharp blade to cut through the coating and into the substrate to produce 5 parallel scribe lines, and repeat at a 45° angle to produce crosshatch lines. The parallel scribe lines are 0.12" apart. Use Tape 250 (3M Co.) type masking tape, apply it to the 45° intersection of the crosshatch lines, and press down firmly using the tape roll. The tape is then removed in one quick but smooth motion perpendicular to the panel and the removal of the coating from the substrate is inspected and scored as outlined in the specification standard. A score of 8 or above is considered passed.

[0079] SIJA Adhesion Testing: Adhesion testing was performed roughly in accordance with BSS 7391 using a single impact jet apparatus (SIJA, Cambridge). The initial apparatus used a 1 mm nozzle configuration and employed a 0.22 diameter 5.5 mm Crosman Accupell tip pellet (#11246). The nozzle-sample distance was fixed at 7 mm. Testing was completed after an overnight immersion in water, using a line laser to locate the impact location and a 45° specimen impact drop geometry. A single water jet was impacted at each location to test adhesion, with the pressure indicated by the "shot" being below its impact. A target velocity of 600 m / s was used for each individual shot. GIMP software was used to evaluate the area removed. A passing score was considered to have a <5 mm 2 of paint removal area.

[0080] Figure 4is a graphic representation of the results of exemplary adhesion testing of the present disclosure. As briefly described above, adhesion testing was performed using a single impact jet apparatus (SIJA, Cambridge) roughly in accordance with BSS 7391. The initial apparatus used a 1 mm nozzle configuration and employed a 0.22 diameter 5.5 mm Crosman Accupell pointed pellet (#11246). Testing was completed after overnight immersion in water, using a line laser to locate the impact location and a 45° specimen impact drop geometry. A single water jet was impacted at each site to test adhesion, with the pressure indication used for the "fire" being lower than its impact. The velocity of each individual shot was recorded for future reference, but the velocity was typically 600 m / s (±25 m / s). GIMP software was used to evaluate the area removed. Passing scores were considered to have <5 mm 2 Two methods of calculating the area are used. An exemplary pass result is shown in image 400. A fail result is shown in image 404, while a borderline result (area 5-10 mm2) is shown in image 402. 2 ).

[0081] Rainwater erosion test :Rain erosion test was performed according to BOEING specification support standard BSS7393. After surface treatment and before coating, PG-777 tape (3M Co.) was used to stick 1.82±0.03 inches from the lower edge of the foil to produce the leading edge of the composite foil for exposure to raindrops. After curing, the foil was immersed in water for 16-24 hours, then loaded into a rotating arm chamber and rotated at an average speed of 385 miles / hour, exposed to 3-4 inches of rain / hour and 1-4mm droplet size simulated rain for about 30 minutes. The sample was then taken out and analyzed.

[0082] Skydrol Hydraulic Fluid Testing : Treated and painted samples (150 mm x 75 mm) were immersed in deionized water or Skydrol (Avial) hydraulic fluid at room temperature for 30 days prior to scratch adhesion testing.

[0083] The results of the various tests of the adhesion promoter compositions are summarized in the following table. Reference will be made to the tables to describe any deviations or changes from the standard procedure.

[0084] Example 1: In this example, sanded BMS8-422 was sprayed with a treatment solution containing only aminosilane or swelling agent. The solvents used in these formulations included 20% DMM, 30% PnP and 50% MIBK. After drying at room temperature for 30 minutes, the samples were cured at 120°C for 30 minutes. The primer and topcoat were sprayed onto the samples according to the above method instructions. Note that the dry scratch adhesion was all better than the sample that was only sanded (no adhesion promoter). However, after 30 days of condensing humidity at 49°C, the scratch adhesion results were a score of <7. These results indicate that silane or swelling agent used alone is not sufficient to improve the adhesion of the topcoat on the coating surface.

[0085] Table 2: Scratch Adhesion Performance of Diffusion-Interlock Adhesion Promoter Formulations Containing Only Aminosilane or Swelling Agents Coated on Sanded BMS8-422 with Primer and Topcoat

[0086]

[0087] Example 2: Adhesion was tested on sanded BMS8-422 with a mixture of CNO and aminosilanes with different methoxy or ethoxy silyl groups. The molar ratio of aminosilane to CNO was 1:1. The solvents used in these formulations included 20% DMM, 30% PnP, and 50% MIBK. The samples were air dried for 30 minutes and then cured in a 120°C oven for half an hour. All formulations except 3-aminopropyldimethylethoxysilane, which is monoethoxy, gave better scratching and SIJA adhesion results than sanding alone. The results show the importance of the presence of more than two alkoxy groups in the silane and the combination of the swelling agent and the silane.

[0088] Table 3: Scratch and SIJA Adhesion of Diffusion-Interlocking Adhesion Promoter Formulations Containing CNO and Aminosilane

[0089]

[0090] Example 3: In the following examples, sanded and unsanded BMS8-399 were spray coated with 3.5% APMDES / BCPhO at an aminosilane:swelling agent molar ratio of 0.5. The solvents used in these formulations included 20% DMM, 30% PnP, and 50% MIBK. The sprayed samples were dried at room temperature for 30 minutes and then cured in an oven for half an hour at temperatures of 100°C, 120°C, and 150°C. For the sanded plus adhesion promoter samples, adhesion passed at all temperatures. However, for the unsanded plus adhesion promoter condition, poor condensing humidity scratch adhesion was observed at the higher temperature of 150°C.

[0091] Table 4: Scratch and SIJA adhesion of diffusion-interlocking adhesion promoter formulations (3.5% AMPDES / BCPhO solution, AMPDES:BCPhO ratio 1:2) on sanded or unsanded BMS8-399 at different cure temperatures

[0092]

[0093] Example 4: In the examples summarized in Table 5, reference was made to the active ingredients (total silane and swelling agent) using adhesion promoter compositions based on 3.5% solutions. These examples were cured at 120°C for 30 minutes. The solvents used in these formulations included 20% DMM, 30% PnP, and 50% MIBK, applied using a two-pass process. The results summarized in Table 5 indicate that a range of silane:swelling agent ratios resulted in adequate adhesion improvement.

[0094] Table 5: Scratch and SIJA Adhesion of Diffusion-Interlocking Adhesion Promoter Formulations with Different Silane:Swelling Agent Ratios

[0095]

[0096] Example 5: In the examples summarized in Table 6, the ratio of silane to swelling agent for all compositions was 0.5:1, and all adhesion promoter formulations were cured at 120°C for 30 minutes. The solvents used in these formulations included 20% DMM, 30% PnP, and 50% MIBK. The addition of the silane APS (aminopropyltriethoxysilane) to the APMDES / BCPhO formulation resulted in a slight improvement in the condensing humidity adhesion score. The ratio of APS to APMDES had no significant effect on the adhesion results.

[0097] Table 6: Scribe and SIJA Adhesion of Diffusion-Interlocking Adhesion Promoter Formulations with Hybrid Silanes

[0098]

[0099] Example 6: As shown, Table 7 includes examples using an aqueous primer (45GY005 chrome-free water-reducible epoxy primer) and a 3.5% APMDES / BCPhO adhesion promoter composition. These examples were cured at 120°C for 30 minutes. The solvents used in these formulations included 20% DMM, 30% PnP, and 50% MIBK. For the adhesion promoter compositions represented by an asterisk (*), 20% APS based on APMDES was added to the adhesion promoter composition. The treatments summarized in Table 7 provided good scratch and SIJA adhesion when using an aqueous primer. The results in Table 7 indicate that there are no significant differences between two or four times (i.e., different thicknesses of adhesion promoter).

[0100] Table 7: Scratch and SIJA adhesion of 3.5% APMDES / BCPhO formulations using an aqueous primer (45GY005 Chrome-free water-reducible epoxy primer) as a surface topcoat

[0101]

[0102] Example 7: In these examples in Table 8, glass fiber reinforced PEKK composite BMS8-429 was used as a substrate. Adhesion promoter solutions with different concentrations, aminosilane-swelling agent ratios and with / without APS (the amount of APS was 20% of APMDES) were sprayed onto the surface. After air drying for 30 minutes, the samples were cured in an oven at 120°C for 30 minutes. Subsequently, organic solvent primer, MSS10-103 Gr A and MSS10-60 Desothane topcoat (CA8000 / B70846 / CA8000B) were applied. After curing for 2 weeks at room temperature, the scratch adhesion and SIJA were tested. All treatments gave good results. All formulations resulted in improved adhesion, indicating that the adhesion promoter formulations resulted in improved adhesion of glass fiber reinforced PEKK.

[0103] Table 8: Adhesion results of adhesion promoter formulations on glass fiber PEKK composite BMS8-429

[0104]

[0105] Example 8: In the examples shown in Table 9, BMS8-399 flat panels and rain erosion foils were coated with various aminosilanes and swelling agents at different concentrations and ratios, and overcoated with primer only or primer and topcoat. The solvents used in these formulations included 20% DMM, 30% PnP, and 50% MIBK. The results show that the selected treatment solutions resulted in improved scratching and SIJA adhesion, and the composites that were sanded, then treated and painted also passed the rain erosion score (above 8 points).

[0106] Table 9: Scratch and SIJA Adhesion, Skydrol Pencil Hardness and Rain Erosion Results for Selected Adhesion Promoter Solutions

[0107]

[0108] Example 9: In the examples with the results in Table 10, all adhesion promoter solutions had a solids content of 5%, with a ratio of APMDES / BCPhO = 0.375, but different solvent systems were used. The AP solution was sprayed onto an unsanded BMS-399 surface. After drying the solvent at room temperature for 30 minutes, the AP layer was further cured in an oven at 120°C for 30 minutes. Primer and topcoat were then applied under normal conditions. Removal area < 5 mm 2 , then SIJA adhesion performance passed. The scratch adhesion after drying and immersion in water for 7 days all exceeded 8 points, and most of them were 10 points. However, after 30 days of condensation humidity testing, the single or dual solvent system scored 5-7, i.e. failed. This example also shows that solvents other than MIBK and PnP are also effective, especially in solvent combinations.

[0109] Table 10: Scratch and SIJA adhesion of 5% based adhesion promoter formulations using APMDES / BCPhO = 0.375 ratio but different carrier solvents

[0110]

[0111] Example 10: In these examples of Table 11, a 5% APS-CNO or APS-CPO solution (wherein the ratio of silane to swelling agent in the mixed solvent was 1:1) was sprayed onto the BMS8-422 surface. After drying in air for 60 minutes, the samples were cured at 120°C for 30 minutes. After coating with PR-1776M B-grade low-weight fuel tank sealant, the assembly was cured at room temperature for 14 days. When adhesion promoter was not applied to both sanded and unsanded samples, there was no adhesion at all between the sealant and PEEK BMS8-422. After coating with adhesion promoter and thermal curing, the adhesion between the sealant and PEEK increased significantly (causing failure within the sealant rather than between the sealant and the composite). All samples treated with adhesion promoter solutions also passed 7 days of salt and jet fuel immersion at 160°F.

[0112] Table 11: Peel adhesion results of sealant on BMS8-422 after application of adhesion promoter, and the effect of immersion in salt solution and jet fuel. Notes: AF: adhesive failure; CF: cohesive failure

[0113]

[0114] Additionally, the present disclosure includes examples according to the following clauses:

[0115] 1. An adhesion promoter composition comprising:

[0116] With the general formula ((RO) n -SiY)m -(CH2) x -A, wherein n = 2-3, m = 1-2, Y is absent (when n = 3) or is a C1-C6 alkyl group, x = 1-8, A = none, NH z , SH or epoxy, z=1-2, and R=C1-C6 alkyl;

[0117] one or more swelling agents; and

[0118] one or more organic solvents;

[0119] The one or more reactive silanes form a complex with the one or more swelling agents through hydrogen bonds and / or ionic bonds.

[0120] 2. The adhesion promoter composition of clause 1, wherein the molar ratio of the one or more reactive silanes to the one or more swelling agents is from about 0.1:1 to about 1.5:1.

[0121] 3. The adhesion promoter composition of any of the preceding clauses, wherein the one or more reactive silanes comprise amine functional groups, epoxy functional groups, mercapto functional groups, isocyanate functional groups, or combinations thereof.

[0122] 4. An adhesion promoter composition as described in any of the preceding clauses, wherein the one or more reactive silanes include: trialkoxysilanes, such as trimethoxysilane, triethoxysilane, tripropoxysilane, etc.; or dialkoxysilanes, such as dimethoxysilane, diethoxysilane, dipropoxysilane; monoalkoxysilanes, such as dimethylmethoxysilane, dimethylethoxysilane, diethylmethoxysilane, diethylethoxysilane; or combinations thereof.

[0123] 5. The adhesion promoter composition of any of the preceding clauses, wherein the one or more reactive silanes comprises a polyalkoxysilane.

[0124] 6. The adhesion promoter composition of any of the preceding clauses, wherein the one or more reactive silanes comprise bis-trimethoxysilane, bis-triethoxysilane, tris-trimethoxysilane, tris-triethoxysilane, or a combination thereof.

[0125] 7. An adhesion promoter composition as described in any of the preceding clauses, wherein the one or more reactive silanes are selected from the group consisting of 3-aminopropyltrimethoxysilane (APTMS), 3-aminopropyltriethoxysilane (APTES), 3-aminopropylmethyldimethoxysilane (APMDMS), 3-aminopropylmethyldiethoxysilane (APMDES), 3-aminopropyldimethylethoxysilane (APDMES), 3-(2-aminoethylamino)propyltrimethoxysilane (AEPTMS), 3-(2-aminoethylamino)propyltriethoxysilane (AEPTES), 3-(2-aminoethylamino)propyldimethoxymethylsilane (AEDMMS), 3-(2-aminoethylamino)propyldiethoxymethylsilane (AEDMES), 3-[2-(2-aminoethylamino)ethylamino]propyltrimethoxysilane (TMSDETA) and 3-[2-(2-aminoethylamino)ethylamino]propyltriethoxysilane (TESDETA).

[0126] 8. An adhesion promoter composition as described in any of the preceding clauses, wherein the one or more reactive silanes are selected from the group consisting of bis[3-(trimethoxysilyl)propyl]amine (BTMSPA), 1,2-bis(trimethoxysilyl)ethane (BTMSE), 1,8-bis(trimethoxysilyl)octane (BTMSO), tris[3-(trimethoxysilyl)propyl]isocyanurate (TMSIC), 1,2-bis(triethoxysilyl)ethane (BTESE), 1,8-bis(triethoxysilyl)octane (BTESO) and bis[3-(triethoxysilyl)propyl]tetrasulfide (BTSTS).

[0127] 9. An adhesion promoter composition as described in any of the preceding clauses, wherein the other functional silanes include (3-glycidoxypropyl)trimethoxysilane (GPTMS), (3-glycidoxypropyl)triethoxysilane (GPTES), [2-(3,4-epoxycyclohexyl)ethyl]trimethoxysilane (ECTMS), [2-(3,4-epoxycyclohexyl)ethyl]triethoxysilane (ECTES), (3-mercaptopropyl)trimethoxysilane (MPTMS), (3-mercaptopropyl)triethoxysilane (MPTES), 3-(trimethoxysilyl)propyl isocyanate (TMSPI) and 3-(triethoxysilyl)propyl isocyanate (TESPI), or a combination thereof.

[0128] 10. The adhesion promoter composition of any of the preceding clauses, wherein the one or more reactive silanes are present in the adhesion promoter composition in an amount of 1 wt% to 10 wt%, based on the total weight of the adhesion promoter composition.

[0129] 11. The adhesion promoter composition of any of the preceding clauses, wherein the one or more swelling agents are present in the adhesion promoter composition in an amount of 1 wt % to 10 wt %, based on the total weight of the adhesion promoter composition.

[0130] 12. An adhesion promoter composition as described in any of the preceding clauses, wherein the one or more swelling agents are selected from the group consisting of phenol or naphthol derivatives, in particular chlorine-substituted phenol or naphthol derivatives, such as 2-chlorophenol (2CPO), 3-chlorophenol (3CPO), 4-chlorophenol (CPhO), 2-amino-4-chlorophenol (ACPO), 2-allyl-4-chlorophenol (AlCPO), 2-benzyl-4-chlorophenol (BCPO), 2-methoxy-4-chlorophenol (MCPO). PO), 4-chloro-1-naphthol (CNO), 2-chloro-1-naphthol (2CNO), 1-chloro-2-naphthol (C2NO), 2,4-dichloro-1-naphthol (DCNO), 2-allyl-4-chloro-1-naphthol (ACNO), 3,3'-dichloro-[1,1'-binaphthyl]-2,2'-diol, 2,2'-methylenebis(4-chlorophenol) (BCPhO), 4,4'-isopropylidenebis(o-chlorophenol), and 2,6-bis(2-hydroxy-5-chlorobenzyl)-4-chlorophenol.

[0131] 13. An adhesion promoter composition as described in any of the preceding clauses, wherein the one or more organic solvents include alcohols, ethers, esters, ketones, such as isopropyl alcohol, butanol, di(propylene glycol) monomethyl ether (DPM), dipropylene glycol dimethyl ether (DMM), propylene glycol monopropyl ether (PnP), dimethyl isosorbide, propylene glycol monomethyl ether acetate (MPA), butyl acetate, amyl acetate, ethylene glycol diacetate, propylene glycol diacetate, methyl isobutyl ketone (MIBK), methyl amyl ketone (MAK), or a combination thereof.

[0132] 14. An adhesion promoter composition comprising:

[0133] With the general formula ((RO) n -SiY) m -(CH2) x -A, wherein n = 2-3, m = 1-2, Y is absent (when n = 3) or is a C1-C6 alkyl group, x = 1-8, A = none, NH z , SH or epoxy, z=1-2, and R=C1-C6 alkyl;

[0134] one or more swelling agents; and

[0135] one or more organic solvents;

[0136] And among them:

[0137] The one or more reactive silanes form a complex with the one or more swelling agents through hydrogen bonds and / or ionic bonds; and

[0138] The molar ratio of the one or more reactive silanes to the one or more swelling agents is from about 0.1:1 to about 1.5:1.

[0139] 15. A composite component comprising:

[0140] Thermoplastic or thermoset composite materials;

[0141] An adhesion promoter composition disposed on the surface of the thermoplastic composite material, comprising:

[0142] one or more reactive silanes; and

[0143] one or more swelling agents;

[0144] wherein the one or more reactive silanes form a complex with the one or more swelling agents through hydrogen bonds and / or ionic bonds; and

[0145] the adhesion promoter composition diffuses into at least a portion of the thermoplastic composite; and

[0146] A surface coating is disposed on the surface of the thermoplastic composite material on which the adhesion promoter is disposed.

[0147] 16. The composite component of clause 15, wherein the one or more reactive silanes can chemically react with the surface coating.

[0148] 17. A composite part according to clause 15 or 16, wherein the thermoplastic composite material comprises polyaryletherketone (PAEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), polyetherimide (PEI), polyimide or a combination thereof.

[0149] 18. The composite component of any one of clauses 15 to 17, wherein the surface coating comprises an epoxy-based polymer formulation, a polyurethane-based polymer formulation, a polythioether-based polymer formulation, or a combination thereof.

[0150] 19. A composite component as described in any of clauses 15 to 18, wherein the one or more reactive silanes are selected from the group consisting of 3-aminopropyldimethylethoxysilane (APDMES), 3-aminopropyltrimethoxysilane (APTMS), 3-aminopropyltriethoxysilane (APTES) and 3-aminopropylmethyldimethoxysilane (APMDMS).

[0151] 20. A composite component as described in any of clauses 15 to 19, wherein the one or more reactive silanes are selected from the group consisting of bis[3-(trimethoxysilyl)propyl]amine (BTMSPA), 1,2-bis(trimethoxysilyl)ethane (BTMSE), 1,8-bis(trimethoxysilyl)octane (BTMSO), tris[3-(trimethoxysilyl)propyl]isocyanurate (TMSIC), 1,2-bis(triethoxysilyl)ethane (BTESE), 1,8-bis(triethoxysilyl)octane (BTESO) and bis[3-(triethoxysilyl)propyl]tetrasulfide (BTSTS).

[0152] 21. A composite component as described in any of clauses 15 to 20, wherein the other functional silanes include (3-glycidyloxypropyl)trimethoxysilane (GPTMS), (3-glycidyloxypropyl)triethoxysilane (GPTES), [2-(3,4-epoxycyclohexyl)ethyl]trimethoxysilane (ECTMS), [2-(3,4-epoxycyclohexyl)ethyl]triethoxysilane (ECTES), (3-mercaptopropyl)trimethoxysilane (MPTMS), (3-mercaptopropyl)triethoxysilane (MPTES), 3-(trimethoxysilyl)propyl isocyanate (TMSPI) and 3-(triethoxysilyl)propyl isocyanate (TESPI) or a combination thereof.

[0153] 22. The composite part of any of clauses 15 to 21, wherein the one or more swelling agents are selected from the group consisting of 4-chloro-1-naphthol (CNO), 4-chlorophenol (CPhO) and 2,2'-methylenebis(4-chlorophenol) (BCPhO).

[0154] 23. A composite part according to any of clauses 15 to 22, wherein the one or more swelling agents are selected from the group consisting of phenol or naphthol derivatives, in particular chlorine-substituted phenol or naphthol derivatives, such as 2-chlorophenol (2CPO), 3-chlorophenol (3CPO), 4-chlorophenol (CPhO), 2-amino-4-chlorophenol (ACPO), 2-allyl-4-chlorophenol (AlCPO), 2-benzyl-4-chlorophenol (BCPO), 2-methoxy-4-chlorophenol (MCPhO). O), 4-chloro-1-naphthol (CNO), 2-chloro-1-naphthol (2CNO), 1-chloro-2-naphthol (C2NO), 2,4-dichloro-1-naphthol (DCNO), 2-allyl-4-chloro-1-naphthol (ACNO), and 3,3'-dichloro-[1,1'-binaphthyl]-2,2'-diol, 2,2'-methylenebis(4-chlorophenol) (BCPhO), 4,4'-isopropylidenebis(o-chlorophenol), and 2,6-bis(2-hydroxy-5-chlorobenzyl)-4-chlorophenol.

[0155] 24. The composite component of any of clauses 15 to 23, wherein the molar ratio of the one or more reactive silanes to the one or more swelling agents is from about 0.1:1 to about 1.5:1.

[0156] 25. A method of applying an adhesion promoter composition comprising:

[0157] contacting a reaction product of the adhesion promoter composition of any one of clauses 1 to 14 onto a surface of a thermoplastic composite material to form a film;

[0158] heating the film;

[0159] Forming an adhesion promoter film of less than 2 microns; and

[0160] A surface coating is applied over the adhesion promoter composition.

[0161] 26. The method of applying an adhesion promoter composition of clause 25, wherein the thermoplastic composite material comprises polyaryletherketone (PAEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), polyetherimide (PEI), polyimide, or a combination thereof.

[0162] 27. The method of applying an adhesion promoter composition according to Clause 25 or 26, wherein the surface coating comprises an epoxy-based polymer formulation, a polyurethane-based polymer formulation, a polythioether-based polymer formulation, or a combination thereof.

[0163] 28. A method of applying an adhesion promoter composition as described in any of clauses 25 to 27, wherein the one or more reactive silanes are selected from the group consisting of 3-aminopropyldimethylethoxysilane (APDMES), 3-aminopropyltrimethoxysilane (APTMS), 3-aminopropyltriethoxysilane (APTES) and 3-aminopropylmethyldimethoxysilane (APMDMS).

[0164] 29. A method of applying an adhesion promoter composition as described in any of clauses 25 to 28, wherein the one or more reactive silanes are selected from the group consisting of bis[3-(trimethoxysilyl)propyl]amine (BTMSPA), 1,2-bis(trimethoxysilyl)ethane (BTMSE), 1,8-bis(trimethoxysilyl)octane (BTMSO), tris[3-(trimethoxysilyl)propyl]isocyanurate (TMSIC), 1,2-bis(triethoxysilyl)ethane (BTESE), 1,8-bis(triethoxysilyl)octane (BTESO) and bis[3-(triethoxysilyl)propyl]tetrasulfide (BTSTS).

[0165] 30. A method of applying an adhesion promoter composition as described in any of clauses 25 to 29, wherein the other functional silanes include (3-glycidoxypropyl)trimethoxysilane (GPTMS), (3-glycidoxypropyl)triethoxysilane (GPTES), [2-(3,4-epoxycyclohexyl)ethyl]trimethoxysilane (ECTMS), [2-(3,4-epoxycyclohexyl)ethyl]triethoxysilane (ECTES), (3-mercaptopropyl)trimethoxysilane (MPTMS), (3-mercaptopropyl)triethoxysilane (MPTES), 3-(trimethoxysilyl)propyl isocyanate (TMSPI) and 3-(triethoxysilyl)propyl isocyanate (TESPI), or a combination thereof.

[0166] 31. A method of applying an adhesion promoter composition as described in any of clauses 25 to 30, wherein the one or more swelling agents are selected from the group consisting of 4-chloro-1-naphthol (CNO), 4-chlorophenol (CPhO) and 2,2'-methylenebis(4-chlorophenol) (BCPhO).

[0167] 32. A method of applying an adhesion promoter composition as described in any of clauses 25 to 31, wherein the one or more swelling agents are selected from the group consisting of phenol or naphthol derivatives, in particular chlorine-substituted phenol or naphthol derivatives, such as 2-chlorophenol (2CPO), 3-chlorophenol (3CPO), 4-chlorophenol (CPhO), 2-amino-4-chlorophenol (ACPO), 2-allyl-4-chlorophenol (AlCPO), 2-benzyl-4-chlorophenol (BCPO), 2-methoxy-4-chlorophenol ( ... phenol (MCPO), 4-chloro-1-naphthol (CNO), 2-chloro-1-naphthol (2CNO), 1-chloro-2-naphthol (C2NO), 2,4-dichloro-1-naphthol (DCNO), 2-allyl-4-chloro-1-naphthol (ACNO), 3,3'-dichloro-[1,1'-binaphthyl]-2,2'-diol, 2,2'-methylenebis(4-chlorophenol) (BCPhO), 4,4'-isopropylidenebis(o-chlorophenol) and 2,6-bis(2-hydroxy-5-chlorobenzyl)-4-chlorophenol.

[0168] 33. A method of applying an adhesion promoter composition as described in any of clauses 25 to 32, wherein the one or more organic solvents include alcohols, ethers, esters, ketones, such as isopropyl alcohol, butanol, di(propylene glycol) monomethyl ether (DPM), dipropylene glycol dimethyl ether (DMM), propylene glycol monopropyl ether (PnP), dimethyl isosorbide, propylene glycol monomethyl ether acetate (MPA), butyl acetate, amyl acetate, ethylene glycol diacetate, propylene glycol diacetate, methyl isobutyl ketone (MIBK), methyl amyl ketone (MAK), or a combination thereof.

[0169] 34. The method of applying an adhesion promoter composition of any one of clauses 25 to 33, wherein applying the adhesion promoter composition to the surface of the thermoplastic composite further comprises coating the adhesion promoter composition onto the surface of the thermoplastic composite.

[0170] 35. The method of applying an adhesion promoter composition of any one of clauses 25 to 34, further comprising heat curing the adhesion promoter at a temperature of about 10°C to about 200°C for about 1 minute to about 120 minutes.

[0171] 36. The method of applying an adhesion promoter composition of any one of clauses 25 to 35, further comprising grinding a surface of the thermoplastic composite material prior to applying the adhesion promoter composition onto the surface of the thermoplastic composite material.

[0172] 37. A method of applying an adhesion promoter composition as described in any one of clauses 25 to 36, wherein the adhesion promoter film is less than 1 micron.

[0173] 38. A method of applying an adhesion promoter composition as described in any one of clauses 25 to 37, wherein the adhesion promoter film is from about 100 nm to about 800 nm.

[0174] 39. A method of applying an adhesion promoter composition as described in any one of Clauses 25 to 38, wherein the surface coating comprises any of an epoxy coating, a polyurethane coating, a sealant or an adhesive.

[0175] Although the present teaching has been described for one or more embodiments, the illustrated examples can be changed and / or modified without departing from the spirit and scope of the appended claims. For example, it is understood that although the process is described as a series of actions or events, the present teaching is not limited to the order of these actions or events. Some actions can occur in different orders and / or occur simultaneously with other actions or events other than those described herein. In addition, not all process stages need to implement the method of one or more aspects or embodiments of the present teaching. It is understood that structural objects and / or processing stages can be added, or existing structural objects and / or processing stages can be removed or modified. In addition, one or more actions described herein can be performed in one or more separate actions and / or stages. In addition, with respect to the terms "including", "comprising", "having", "with" or their variants used in the specification and claims, these terms are intended to be inclusive in a manner similar to the term "including". The term "at least one" is used to indicate that one or more of the listed items can be selected. In addition, in the discussion and claims herein, the term "on" used with respect to two materials, one "on" the other "on", means that there is at least some contact between the materials, while "above" means that the materials are close, but there may be one or more other intermediate materials, so that contact is possible but not required. Neither "on" nor "above" as used herein implies any directionality. The term "conformal" describes a coating in which the angle of the underlying material is maintained by a conformal material. The term "about" indicates that the listed values ​​can be slightly changed, as long as the change does not cause the process or structure to be inconsistent with the embodiment shown. The terms "engage", "engage", "connect", "connected" and "connected with..." mean "directly connected with..." or "connected with..." via one or more intermediate elements or members. Finally, the term "exemplary" or "illustrative" indicates that the description is used as an example, rather than implying that it is ideal. Other embodiments of the present teaching may be obvious to those skilled in the art in view of the specification and practice disclosed herein. The description and embodiments should be considered as exemplary only, and the true scope and spirit of the present teaching are shown by the appended claims.

Claims

1. An adhesion promoter composition comprising: With the general formula ((RO) n -SiY) m -(CH2) x -A one or more reactive silanes, wherein, n=2-3, m=1-2, Y is absent (when n=3) or is C1-C6 alkyl, x=1-8, A=none, NH z , SH or epoxy, z=1-2, and R=C1-C6 alkyl; one or more swelling agents; and one or more organic solvents; The one or more reactive silanes form a complex with the one or more swelling agents through hydrogen bonds and / or ionic bonds.

2. The adhesion promoter composition according to claim 1, wherein The molar ratio of the one or more reactive silanes to the one or more swelling agents is from about 0.1:1 to about 1.5:

1.

3. The adhesion promoter composition according to claim 1 or 2, wherein: The one or more reactive silanes include amine functional groups, epoxy functional groups, mercapto functional groups, isocyanate functional groups, or combinations thereof.

4. The adhesion promoter composition according to any one of claims 1 to 3, wherein The one or more reactive silanes include: trialkoxysilanes, such as trimethoxysilane, triethoxysilane, tripropoxysilane, etc.; or dialkoxysilanes, such as dimethoxysilane, diethoxysilane, dipropoxysilane; monoalkoxysilanes, such as dimethylmethoxysilane, dimethylethoxysilane, diethylmethoxysilane, diethylethoxysilane; or combinations thereof.

5. The adhesion promoter composition according to any one of claims 1 to 4, wherein The one or more reactive silanes include polyalkoxysilanes.

6. The adhesion promoter composition according to any one of claims 1 to 5, wherein The one or more reactive silanes include bis-trimethoxysilane, bis-triethoxysilane, tris-trimethoxysilane, tris-triethoxysilane, or a combination thereof.

7. The adhesion promoter composition according to any one of claims 1 to 6, wherein The one or more reactive silanes are selected from the group consisting of 3-aminopropyltrimethoxysilane (APTMS), 3-aminopropyltriethoxysilane (APTES), 3-aminopropylmethyldimethoxysilane (APMDMS), 3-aminopropylmethyldiethoxysilane (APMDES), 3-aminopropyldimethylethoxysilane (APDMES), 3-(2-aminoethylamino)propyltrimethoxysilane (AEPTMS), 3-(2-aminoethylamino)propyltriethoxysilane (AEPTES), 3-(2-aminoethylamino)propyldimethoxymethylsilane (AEDMMS), 3-(2-aminoethylamino)propyldiethoxymethylsilane (AEDMES), 3-[2-(2-aminoethylamino)ethylamino]propyltrimethoxysilane (TMSDETA) and 3-[2-(2-aminoethylamino)ethylamino]propyltriethoxysilane (TESDETA).

8. An adhesion promoter composition comprising: With the general formula ((RO) n -SiY) m -(CH2) x -A one or more reactive silanes, wherein, n=2-3, m=1-2, Y is absent (when n=3) or is C1-C6 alkyl, x=1-8, A=none, NH z , SH or epoxy, z=1-2, and R=C1-C6 alkyl; one or more swelling agents; and one or more organic solvents; And among them: The one or more reactive silanes form a complex with the one or more swelling agents through hydrogen bonds and / or ionic bonds; and The molar ratio of the one or more reactive silanes to the one or more swelling agents is from about 0.1:1 to about 1.5:

1.

9. A composite component comprising: Thermoplastic or thermoset composite materials; An adhesion promoter composition disposed on the surface of the thermoplastic composite material, comprising: one or more reactive silanes; and one or more swelling agents; wherein the one or more reactive silanes form a complex with the one or more swelling agents through hydrogen bonds and / or ionic bonds; and the adhesion promoter composition diffuses into at least a portion of the thermoplastic composite; and a surface coating disposed on the surface of the thermoplastic composite material on which the adhesion promoter has been disposed.

10. A method of applying an adhesion promoter composition, comprising: contacting a reaction product of the adhesion promoter composition of any one of claims 1 to 7 onto a surface of a thermoplastic composite material to form a film; heating the film; Forming an adhesion promoter film of less than 2 microns; and A surface coating is applied over the adhesion promoter composition.

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