Adhesion promoter for composites and method of manufacturing the same

Abstract

To provide an adhesion promoter composition that is effective and practical in achieving sufficient adhesion, alone or in combination with surface treatment methods such as sanding.SOLUTION: An adhesion promoter composition is provided which comprises: one or more reactive silanes having a general formula ((RO)n-SiY)m-(CH2)x-A [where n=2-3; m=1-2; Y does not exist (when n=3) or is a C1-C6 alkyl group; x=1-8; A=none, NHz, SH, or epoxy; z=1-2; and R=C1-C6 alkyl]; one or more swelling agents; and one or more organic solvents; where the one or more reactive silanes forms a complex with the one or more swelling agents through hydrogen bonding and / or ionic bonding. Also provided is a composite part, comprising: a thermoplastic or thermoset composite; an adhesion promoter composition disposed upon a surface of the thermoplastic composite; and a surface coating disposed upon a surface of the thermoplastic composite where the adhesion promoter has been disposed.SELECTED DRAWING: None

Description

[Technical field]

[0001]

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

[0002]

[0002] Polyaryletherketone (PAEK) thermoplastic composites have desirable bulk properties for several applications in aerospace and other industries. These PAEK composites are incompatible with currently qualified aerospace finishes that were originally developed for metal and thermoset substrate materials. Finishes, sealants, and surface coatings play a critical role in the successful assembly of various aircraft components and are widely used in both manufacturing and maintenance.

[0003]

[0003] Unfortunately, coatings, sealants, and adhesives that provide acceptable adhesion on thermoset materials fail to meet the same adhesion requirements when applied to polyaryletherketone (PAEK), polyetherketoneketone (PEKK), polyetheretherketone (PEEK), and other thermoplastic or thermoplastic composite materials after surface preparation by sanding. Adhesion of these finishes to thermoplastic materials can be achieved using surface preparation methods other than sanding, but in repair and rework situations, sanding is the most practical surface preparation technique.

[0004]

[0004] There is an interest in developing effective and practical chemical treatments to achieve sufficient adhesion, either alone or in combination with other surface preparation methods for aerospace composites, including but not limited to sanding. Summary of the Invention

[0005]

[0005] The following presents a simplified summary in order to provide a basic understanding of some aspects of one or more embodiments of the present teachings. This summary is not an extensive overview, and is not intended to identify key or critical elements of the present teachings or to delineate the scope of the present disclosure. Rather, its primary purpose is merely to present one or more concepts in a simplified form as a prelude to the more detailed description that is presented later.

[0006]

[0006] An adhesion promoter composition is disclosed. The adhesion promoter composition includes one or more reactive silanes, one or more swelling agents, and one or more organic solvents, where the one or more reactive silanes form a complex with the one or more swelling agents. Embodiments of the adhesion promoter composition include those where the one or more reactive silanes form a complex with the one or more swelling agents through interactions such as hydrogen bonding and / or ionic bonding. The molar ratio of the one or more reactive silanes to the one or more swelling agent functional groups is about 0.1:1 to about 1.5:1. The one or more reactive silanes may include amine functional groups, epoxy functional groups, mercapto functional groups, isocyanate functional groups, or combinations thereof. The one or more reactive silanes may include multialkoxysilanes. The one or more reactive silanes may include bis-trimethoxysilane, bis-triethoxysilane, tris-trimethoxysilane, tris-triethoxysilane, or combinations thereof. The one or more reactive silanes are selected from the group comprising 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).The one or more reactive silanes are selected from the group that 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 combinations thereof. The one or more reactive silanes are present in the adhesion promotion 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 from 1 wt % to 10 wt %, based on the total weight of the adhesion promoter composition.The one or more swelling agents may be 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 The phenol or naphthol derivatives, in particular chloro-substituted phenol or naphthol derivatives, are selected from the group comprising phenol or naphthol derivatives, such as o-naphthol (DCNO), 2-allyl-4-chloro-1-naphthol (ACNO), and 3,3'-dichloro-[1,1'-binaphthalene]-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 an alcohol, an ether, an ester, a ketone, such as isopropanol, butyl alcohol, di(propylene glycol) peach methyl ether (DPM), dipropylene glycol dimethyl ether (DMM), propylene glycol monopropyl ether (PnP), dimethyl isosorbide, propylene glycol monomethyl ether acetate (MPA), butyl acetate, pentyl acetate, ethylene glycol diacetate, propylene glycol diacetate, methyl isobutyl ketone (MIBK), methyl amyl ketone (MAK), or a combination thereof.

[0007] A composite part is disclosed. The composite part includes a thermoplastic composite and an adhesion promoter composition disposed on a surface of the thermoplastic composite, the adhesion promoter composition may include one or more reactive silanes and one or more swelling agents, where the one or more reactive silanes form a complex with the one or more swelling agents. The composite part also includes a case where the adhesion promoter composition diffuses into at least a portion of the thermoplastic composite. The composite part also includes a surface coating disposed on a surface of the thermoplastic composite on which the adhesion promoter is disposed. An embodiment of the composite part may include a case where the one or more reactive silanes form a complex through interactions such as hydrogen bonding and / or ionic bonding with the one or more swelling agents. The one or more reactive silanes may form a chemical reaction with the surface coating. The thermoplastic composite may include polyaryletherketone (PAEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), polyetherimide (PEI), polyimide, or combinations thereof. The surface coating may include an epoxy-based polymer formulation, a polyurethane-based polymer formulation, a polysulfide-based polymer formulation, or a combination thereof. The one or more reactive silanes are selected from the group including 3-aminopropyldimethylethoxysilane (APDMES), 3-aminopropyltrimethoxysilane (APTMS), 3-aminopropyltriethoxysilane (APTES), and 3-aminopropylmethyldimethoxysilane (APMDMS). The one or more reactive silanes are selected from the group including 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 combinations thereof. The one or more swelling agents are selected from the group including 4-chloro-1-naphthol (CNO), 4-chlorophenol (CPhO), and 2,2'-methylenebis(4-chlorophenol) (BCPhO). The one or more swelling agents may be 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 The reactive silane or silanes are selected from the group comprising phenol or naphthol derivatives, in particular chloro-substituted phenol or naphthol derivatives, such as 3,3'-dichloro-[1,1'-binaphthalene]-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 reactive silane or silanes to the swelling agent or silanes is from about 0.1:1 to about 1.5:1.

[0008]

[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, which may include dipropylene glycol dimethyl ether (DMM), propylene glycol propyl ether (PnP), methyl isobutyl ketone (MIBK), or combinations thereof, to prepare an adhesion promoter composition. The method includes applying the adhesion promoter composition onto a surface of a thermoplastic material or a thermoplastic composite. The method also includes applying a surface coating over the adhesion promoter composition.

[0009] The method for applying the adhesion promoter composition may include heat 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 for applying the adhesion promoter composition may include sanding the surface of the thermoplastic material or thermoplastic composite prior to applying the adhesion promoter composition onto the surface of the thermoplastic material or thermoplastic composite.

[0010]

[0010] The above features, functions, and advantages may be realized alone in various embodiments or may be combined in other embodiments, further details of which may be understood by reference to the following description.

[0011]

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

[0012] [Figure 1]

[0012] A schematic diagram of a transporter according to the present disclosure is shown. [Diagram 2]

[0013] FIG. 1 is a schematic diagram of a diffusion coupling surface treatment approach according to the present disclosure. [Diagram 3]

[0014] FIG. 2 is a flow diagram illustrating a method for applying an adhesion promoter composition according to the present disclosure. [Figure 4]

[0015] 1 is an image of the painted SIJA bonded panel after adhesion testing. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0013]

[0016] It should be noted that some of the details in the drawings have been simplified and drawn to facilitate understanding of the present disclosure, rather than to maintain strict structural accuracy, detail, and scale.

[0014]

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

[0015]

[0018] It would be beneficial to develop a chemical treatment, alone or in combination with other surface treatment methods for aerospace composites, that provides effective and practical adhesion promotion to achieve sufficient adhesion in thermoplastic composites. The adhesion promotion method should be suitable for complex geometries, meet environmental health and safety standards, be compatible with the surface preparation of composites for paint, sealant, adhesive, or surface coating applications, and can optionally be combined with physical surface treatment techniques such as sanding or polishing to be effective.

[0016]

[0019] Additional requirements for an adhesion promoter or adhesion promoter composition for such applications include meeting adhesion requirements, minimizing or eliminating adverse effects on the cure of subsequent finishes, risk of structural damage to the composite, and weight gain. Additionally, the adhesion promoter composition should have stability, a pot life of at least 4 hours, a sufficient overcoat window to allow for manual application of subsequent finishes, and convenient and easy application.

[0017]

[0020] The present disclosure provides an adhesion promoter composition comprising one or more reactive silanes, one or more swelling agents, and one or more organic solvents, where the one or more reactive silanes form a complex with the one or more swelling agents. In an embodiment, a composite part comprising a thermoplastic material or a thermoplastic composite can incorporate one or more adhesion promoter compositions as described herein. In such a composite, application of the adhesion promoter composition can cause the adhesion promoter composition to diffuse into at least a portion of the thermoplastic material or thermoplastic composite and improve the adhesion of a surface coating deposited on one or more surfaces of the thermoplastic material or thermoplastic composite on which the adhesion promoter is deposited. The present disclosure further provides a method of applying an adhesion promoter composition, the method comprising: contacting a reactive silane compound comprising an amine functional group, a swelling agent, and one or more organic solvents comprising dipropylene glycol dimethyl ether (DMM), propylene glycol propyl ether (PnP), methyl isobutyl ketone (MIBK), or combinations thereof to prepare an adhesion promoter composition; applying the adhesion promoter composition onto a surface of a thermoplastic composite via one or more of automated or manual application techniques; and applying a surface coating over the adhesion promoter composition.

[0018]

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

[0019]

[0022] When used throughout, ranges are used as a shorthand notation for any and all values ​​within the range. Any value within the range can be selected as the terminus of the range. In addition, all references cited herein are incorporated by reference in their entirety. In the event of a conflict between the provisions of this disclosure and those of the cited references, the provisions of this disclosure shall prevail.

[0020]

[0023] Unless otherwise specified, all percentages and amounts given herein should be understood to refer to percent by weight. The amounts given are based on the effective weight of the material.

[0021]

[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 of less than 10.0 wt.%, less than 5.0 wt.%, less than 3.0 wt.%, less than 1.0 wt.%, less than 0.1 wt.%, less than 0.05 wt.%, less than 0.01 wt.%, less than 0.005 wt.%, or less than 0.0001 wt.%, based on the total weight of the composition, component, or phase.

[0022]

[0025] In addition, all numerical values ​​are "about" or "approximately" the stated numerical value, taking into account experimental error and experimental variation that one of ordinary skill in the art would expect. It should be recognized that all numerical values ​​and ranges disclosed herein are approximate numerical values ​​and approximate ranges. The terms "about," "substantial," and "substantially" or "approximately" in connection with quantities or measurements mean that the recited characteristic, parameter, or value need not be exactly achieved. Rather, deviations or variations (including, for example, tolerances, measurement errors, measurement accuracy limits, and other factors known to those of ordinary skill in the art) may occur without eliminating the effect intended to be brought about by the characteristic. As used herein, "about" means within ±5% of the stated target value, maximum, or minimum value.

[0023]

[0026] All references cited herein are incorporated by reference in their entirety. In the event of a conflict between the provisions of this disclosure and those of a cited reference, the provisions of this disclosure will control.

[0024]

[0027] The present disclosure provides one or more adhesion promoter compositions. As used herein, the term "adhesion promoter" refers to a group of materials composed of liquid reactive silanes and other additives in an organic solvent. The adhesion promoter compositions disclosed herein include one or more optional swelling agents that can improve or are configured to improve conventional methods of preparing a surface for treatment or application of a coating, paint, or sealant. For example, as further described herein, the adhesion promoter compositions disclosed herein can be capable or configured to simultaneously penetrate and / or swell into one or more top layers of a surface and provide a chemical or physical interlocking component with the surface and one or more components in the adhesion promoter composition. The adhesion promoter compositions disclosed herein can also provide improved adhesion between a surface coating, such as an adhesive or sealant, and a composite material, as compared to currently known adhesives or adhesion promoters known in the art.

[0025]

[0028] The present disclosure provides adhesive compositions and application methods to provide suitable adhesion to complex geometries, compositions that meet various regulatory approvals related to environmental health and safety, and inherent removal of residual mold release agents or other factory contaminants from the composite part surface. Additionally, the adhesion promoters of the present teachings can be optionally removed by physical surface preparation techniques, such as solvent wipes with isopropyl alcohol or other cleaning solvents, grit blasting, sandpaper or mild abrasives, such as Scotch-Brite, to achieve effectiveness. TM Further features of the present disclosure include adhesion promoter compositions that do not adversely affect the cure of subsequent finishes, do not risk structural damage to any composite, add minimal weight, are stable, have sufficient pot life, and have a short minimum overcoat time at ambient temperature.

[0026]

[0029] 1 illustrates a schematic diagram of a vehicle 100, according to an embodiment. As illustrated, 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 an automobile, a boat, a train, etc. In still other embodiments, the systems and methods described below may not be implemented in a vehicle, but rather in a building.

[0027]

[0030] The vehicle 100 may include one or more restrooms (one shown at 110). The restroom 110 may include a sink 112, a toilet 114, and a sensor 116. The sensor 116 may sense / determine whether the restroom 110 is in use (e.g., by a passenger) or vacant. For example, the sensor 116 may be or include a motion sensor. The vehicle 100 may also include one or more kitchens or galleys (one shown at 120). The kitchen 120 may include a sink 122, a dishwasher 124, and an ice maker 126. On or within one or more interior or exterior surfaces or components 128, 130, 132 of the vehicle 100, a composite material comprising an adhesion promoter composition as described herein or a method of application thereof may be applied to improve adhesion between composite layers or coatings thereon. One or more of 128, 130, 132 may include, for example, an adhesion promoter composition used in applying to one or more layers or in improving adhesion between the composite material and one or more applied coatings or sealants.

[0028]

[0031] Examples of polymeric materials that may be used (e.g., as a substrate) to receive surface coating with the adhesion promoter composition and / or subsequent surface coating layer according to the present disclosure include polymeric materials in combination with one or more types of fibers to act as a matrix. In one example, materials useful in the practice of the present disclosure include fiber reinforced plastics (FRPs) that include polymeric materials in combination with inorganic fibers, such as carbon fibers, carbon nanotubes, graphite, glass fibers, glass, metal, metal alloy, or metallized fibers, and metal-coated glass fibers, alumina fibers, or boron fibers. In one example, the fiber reinforced plastics may include organic fibers, such as nylon fibers or aramid fibers. In one example, the fiber reinforced plastics may include organic and / or inorganic fibers blended with a thermosetting material or an epoxy.

[0029]

[0032] In one embodiment, carbon fiber reinforced plastics (CFRP) or glass fiber reinforced plastics (GFRP), as well as polymeric molded articles made therefrom, are imparted with improved interlayer adhesion through the use or application of an adhesion promoter composition suitable for aircraft structures, etc. However, the present disclosure is not limited to these types of materials, and molded articles formed from other polymers may also be used in the presently disclosed processes of the present disclosure.

[0030]

[0033] A component, part, or composite part, such as a carbon fiber reinforced polymer (CFRP) part, is first laid down in multiple layers collectively referred to as a "preform." The term "uncured composite part" or "preform" as used herein refers to one or more plies of composite material impregnated with uncured or sometimes partially cured resin. For example, the uncured composite part may be a fiber reinforced uncured thermoset polymer composite part. While the individual fibers within each layer of the preform may be aligned parallel to one another, different layers may exhibit different fiber orientations that enhance the strength of the resulting composite part along different dimensions. The preform contains a viscous resin that solidifies, and the preform may be solidified into a composite part (e.g., for use in an aircraft). Carbon fiber plies impregnated with uncured thermoset or thermoplastic resin are referred to as "prepregs." As used herein, the term "prepregs" refers to a pre-impregnated stack of composite plies, such as epoxy-impregnated unidirectional composite tapes, woven plies, or chopped versions thereof. Prepregs can be flexible until cured, often by curing with heat and pressure or 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 can be infused with resin before curing. For thermosetting resins, solidification is a one-way process called curing, while for thermoplastic resins, the resin may return to a reformable or viscous form when reheated.

[0031]

[0034] With respect to fiber reinforced thermoset polymer composite parts, curing generally refers to the application of heat and / or pressure to crosslink and consolidate the fibers of the fiber reinforced thermoset polymer composite part. Thermosets can be partially cured (i.e., crosslinked) without the application of pressure, often resulting in an underconsolidated part. Thus, as used herein, the terms "curing" and "curing" include both the application of heat (to cure / crosslink) and pressure (to consolidate) to a fiber reinforced thermoset polymer composite part, such as the thermoset composite parts of the present disclosure.

[0032]

[0035] In some embodiments, the composite part is cured by subjecting it to heat and / or pressure. The heat and / or pressure can be applied according to a predetermined curing schedule that specifies the pressure, temperature, and the duration the pressure and / or temperature are maintained. In some embodiments, the composite part is cured by pressure alone. For example, the composite part can be cured at room temperature with the application of pressure. The pressure can be positive or negative. Adhesion promoter compositions can be used either on one or more surfaces or between layers in the manufacture or processing of such composite parts, at least for the purpose of improving adhesion between layers, or to improve adhesion of surface coatings on the composite or part. Composite materials incorporating thermosetting resins can be applicable to the adhesive formulations described in this disclosure, but also to thermoplastic materials.

[0033]

[0036] FIG. 2 is a schematic diagram of the described adhesion promoter technology, referred to as the "diffusion coupling surface treatment approach" according to the present disclosure. Diffusion coupling surface treatment is a concept based on the swelling of a thin surface layer of polymer and the subsequent interaction of reactive silanes or other crosslinking chemicals, which can form an interfacial crosslinked network and a strengthened adhesion layer. These interfacial crosslinked networks can be generated by the formation of complexes between one or more reactive silanes or other crosslinking chemicals and one or more swelling agents through interactions such as hydrogen bonds and / or covalent bonds. The diffusion coupling approach is based on the chemical inertness of the polymer backbone of PAEK and other thermoplastic or thermoset composites and the need for adhesion enhancement by both chemical and physical means using a common approach. An example of the diffusion coupling approach is depicted in FIG. 2. The proposed mechanism 200 has three stages. First, the diffusion of the active component (in this case an aminosilane 202, APS in this example) and the swelling agent 204 allows the adhesion promoter composition to penetrate the surface and subsurface layers. Therefore, the sublayer needs to swell to some extent in order for the active component to penetrate into its sublayer. Next, crosslinking 206 of the active components through sol-gel hydrolysis and condensation reactions or other crosslinking mechanisms such as covalent or hydrogen bonding forms a composite 208, providing interlocking and enhancing adhesion. Finally, the active layer provides a strong bond to a coating, sealant, or another surface finish through reaction 210 or interaction between the active functional groups and the reactive chemicals of the surface finish, or through molecular entanglements / networks. In examples, the adhesion promoter can form an interpenetrating polymer network (IPN) within the adhesion promoter composition or interpenetrate with the composite surface through its components. An interpenetrating polymer network (IPN) refers to a polymer or polymer layer that includes at least two polymer networks that are at least partially reacted with each other. In the adhesion promoters of the present teachings, the reactive silane and the swelling agent interact to form an IPN through hydrolysis and condensation. In examples that include amine functional groups, the amine groups can also react with a primer, which can be applied after the adhesion promoter composition.Two or more networks may be considered to be physically and possibly chemically entangled, but usually irreversible. In the example shown in FIG. 2, the swelling agent is 4-chloronaphthalene (CNO), a known good solvent for PEEK and other PAEKs. The active ingredient is 3-aminopropyltriethoxysilane (APS). Because CNO is a weak acid and aminosilane is a weak base, the aminosilane 202 and the swelling agent 204 can form hydrogen or ionic bonds, which induces network formation and prevents volatilization of the CNO or silane. After exposure to atmospheric moisture (or by pre-injecting the silane with water), the silane undergoes hydrolysis 210 and condensation to form a sol-gel-like structure. The active ingredient is generally about 5% or less in the mixed solvent solution to form a very thin film on the composite surface.

[0034]

[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, where 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 multifunctional silicon-containing molecules that include reactive functional groups and one or more hydrolyzable alkoxy groups, but are not necessarily limited thereto. Exemplary silanes include, but are not limited to, amine-functional silanes, epoxy-functional silanes, mercapto-functional silanes, isocyanurate-functional silanes, multialkoxy-functional silanes, or combinations thereof. In addition, exemplary silanes may include trialkoxysilanes such as trimethoxy, triethoxy, tripropoxy, etc.; dialkoxysilanes such as dimethoxy, diethoxy, dipropoxy, etc.; monoalkoxysilanes such as dimethylmethoxy, dimethylethoxy, diethylmethoxy, diethylethoxy, etc., or combinations thereof.

[0035]

[0038] Exemplary amine functional silanes 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)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), 3- 3-aminopropyltris(2-(2-methoxyethoxy)ethoxy)silane, 3-aminopropyltriisopropenyloxysilane, 3-aminopropyltri(butanone oximo)silane, 4-aminobutyltriethoxysilane, N-2-(aminoethyl)-3-aminopropyltris(2-ethylhexoxy)silane, 3-aminopropyldimethylethoxysilane, 3-aminopropyldiisopropylethoxysilane, p-aminophenyltrimethoxysilane, m-aminophenyltrimethoxysilane, 3-aminopropylphenyldiethoxysilane, and cyclic azasilanes, such as 2,2-diaminopropyltris(2-methoxyphenyl)phenyl, 3-aminopropyltris(2-methoxyphenyl)phenyl ... and cyclic azasilanes, such as 2,2-diaminopropyltris(2-methoxyphenyl)phenyl, and Methoxy-1,6-diaza-2-silacyclooctane, 2,2-dimethoxy-Nn-butyl-1-aza-2-silacyclopentane, 2,2-diethoxy-1-aza-2-silacyclopentane, 2,2-dimethoxy-Nt-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 combinations thereof.

[0036]

[0039] Exemplary glycidoxy- or epoxy-functional silanes include, but are not limited to, glycidoxypropyltrialkoxysilanes (e.g., glycidoxypropyltrimethoxysilane, (3-glycidyloxypropyl)trimethoxysilane (GPTMS), (3-glycidyloxypropyl)triethoxysilane (GPTES), etc.), 3-(2,3-epoxypropoxypropyl)methyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethylenedioxysilane, 2-(2,3-epoxypropoxypropyl)methyldieth ... trimethoxysilane, 3-(2,3-epoxypropoxypropyl)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-disilapropane, or combinations thereof.

[0037]

[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.

[0038]

[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-isocyanatopropyl trimethoxysilane, 3-isocyanatopropyl trimethoxysilane, isocyanatopropylmethyldimethoxysilane, 3-isocyanatopropyl methyldiethoxysilane, isocyanatomethyl trimethoxysilane, isocyanatomethyl trimethoxysilane, or combinations thereof.

[0039]

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

[0040]

[0043] Further exemplary silanes may include, but are not limited to, bis(trimethoxysilylethyl)benzene, bis(triethoxysilylethyl)benzene, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, vinyl trimethoxysilane, allyl trimethoxysilane, or combinations thereof.

[0041]

[0044] In embodiments of the adhesion promoter composition, when the composition includes multiple reactive silanes, it is 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, providing additional potential reactive functional groups present in the adhesion promoter composition. Without being bound to a particular theory, the additional functional group chemistry within the adhesion promoter composition may provide versatility or utility for the adhesion promoter composition to be used in a number of applications with respect to swelling agents, polymer composites, substrates, surface coatings, or combinations thereof.

[0042]

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

[0043]

[0046] The swelling agent of the present teachings is added to the adhesion promoter to provide at least partial swelling of the surface or sublayer as at least one or more active ingredients and to penetrate the layer or sublayer. The swelling agent further comprises functional groups that can be linked or crosslinked via sol-gel or other crosslinking mechanisms such as covalent or hydrogen bonds to form a complex to provide interlocking and enhance adhesion when using the adhesion promoter composition described herein.

[0044]

[0047] Exemplary swelling agents for use in the adhesion promoter compositions 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. Further examples of swelling agents include, but are not limited to, phenol or naphthol derivatives, chloro-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 (CNO), 2-chloro- These may include 1-naphthol (2CNO), 1-chloro-2-naphthol (CNO), 2,4-dichloro-1-naphthol (DCNO), 2-allyl-4-chloro-1-naphthol (ACNO), and 3,3'-dichloro-[1,1'-binaphthalene]-2,2'-diol, 2,2'-methylenebis(4-chlorophenol) (BCPhO), 4,4'-isopropylidenebis(o-chlorophenol), 2,6-bis(2-hydroxy-5-chlorobenzyl)-4-chlorophenol, or combinations thereof.

[0045]

[0048] The swelling agent(s) may be present in an amount of about 0.01% to about 10% by weight based on the total weight of the adhesion promoter composition. For example, the swelling agent(s) may be present in an amount of about 0.1%, about 0.5%, about 1%, about 1.5%, about 2%, about 3%, about 4%, or about 5% to about 6%, about 6.5%, about 7%, about 8%, about 9%, or about 10% by weight based on the total weight of the adhesion promoter composition. In another example, the swelling agent(s) may be present in an amount of about 0.1% to about 10%, about 2% to about 8%, or about 4% to about 6% by weight based on the total weight of the adhesion promoter composition.

[0046]

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

[0047]

[0050] The one or more organic solvents of the adhesion promoter composition may be or may be configured to disperse, solubilize, solvate, or otherwise dissolve one or more substances or components of the adhesion promoter composition. The one or more organic solvents of the adhesion promoter composition may also be or may be configured to disperse, solubilize, solvate, or otherwise dissolve one or more substances, such as grease, oil, or debris, on a surface that comes into contact with the adhesion promoter composition. For example, the one or more organic solvents of the adhesion promoter composition may be or may be configured to dissolve one or more reactive silanes, one or more swelling agents, any additional functional additives, or a combination thereof. The one or more organic solvents may also be or may be configured to prepare the surface for subsequent treatment or application of a surface coating. For example, the one or more organic solvents may be or may be configured to at least partially provide a cleaning treatment or enhance the swelling properties of a swelling agent when in contact with a surface or substrate to be treated with a coating. It should be understood that any organic solvent capable of or configured to dissolve one or more components of the adhesion promoter composition and / or prepare a surface for the application of a subsequent surface treatment or coating may be utilized.

[0048]

[0051] The one or more organic solvents may be or may include, but are not limited to, aliphatic hydrocarbons, aromatic compounds such as aromatic hydrocarbons, halogenated hydrocarbons, nitrated hydrocarbons, ketones, amines, esters, alcohols, aldehydes, ethers, and the like, or combinations thereof.

[0049]

[0052] Exemplary aliphatic hydrocarbons that may be utilized 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 their congeners, 2,2,4-trimethyl pentane, and the like, cyclohexane, turpentine, limonene, or any combination thereof.

[0050]

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

[0051]

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

[0052]

[0055] Exemplary ketone organic solvents can be or can 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.

[0053]

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

[0054]

[0057] Exemplary alcohols that may be utilized as the one or more organic solvents may be or include, but are not limited to, methanol, ethanol, n-propanol, isopropanol, n-butanol, i-butanol, s-butanol, n-amyl alcohol, i-amyl alcohol, cyclohexanol, n-octanol, ethanediol, diethylene glycol, 1,2-propanediol, and the like, or combinations thereof.

[0055]

[0058] Exemplary ethers that may be utilized as the one or more organic solvents may be or may 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, such as the GALDEN® lineup (commercially available from Solvay, Houston, Texas), or combinations thereof.

[0056]

[0059] The amount of the one or more organic solvents present in the adhesion promoter composition may be from about 75% to about 99.5% by weight based on the total weight of the adhesion promoter composition. For example, the amount of the one or more organic solvents present in the adhesion promoter composition may be from about 75% by weight, about 80% by weight, about 85% by weight, or about 90% by weight to about 95% by weight, about 98% by weight, about 99% by weight, or about 99.5% by weight based on the total weight of the adhesion promoter composition. In another embodiment, the amount of the one or more organic solvents present in the adhesion promoter composition may be from about 75% by weight to about 99.5% by weight, from about 80% by weight to about 99% by weight, from about 85% by weight to about 95% by weight, or from about 85% by weight to about 90% by weight based on the total weight of the adhesion promoter composition. In another embodiment of the adhesion promoter composition, the solvent may be present in an amount of about 25% by weight, about 30% by weight, about 35% by weight, or about 40% by weight based on the total weight of the adhesion promoter composition. In other examples, the solvent may be present in an amount from about 25% to about 40% by weight, from about 25% to about 30% by weight, or from about 30% to about 40% by weight.

[0057]

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

[0058]

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

[0059]

[0062] FIG. 3 is a flow diagram illustrating a method for applying an adhesion promoter composition according to the present disclosure. The method for applying the adhesion promoter composition 300 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 propyl ether (PnP), methyl isobutyl ketone (MIBK), or a combination thereof to prepare an adhesion promoter composition 302, applying the adhesion promoter composition on a surface of a thermoplastic composite 304, and applying a surface coating 306 over the adhesion promoter composition. The surface coating may require an additional application of a primer prior to application of the surface coating, paint, or composition including a polymer. The surface coating may include an epoxy-based polymer formulation, a polyurethane-based polymer formulation, a polysulfide-based polymer formulation, or a combination thereof. The method for applying the adhesion promoter composition may include where the thermoplastic component comprises polyaryletherketone (PAEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), polyetherimide (PEI), polyimide, or combinations thereof. Additional examples of suitable materials or composites may include polyamides, polyimides, poly(amideimides), polyetherimides (PEI), and other high melting point thermoplastics. The adhesion promoter composition used in the method for applying the adhesion promoter composition may include ingredients or ingredients as described herein. The application of the adhesion promoter composition onto the surface of the thermoplastic composite may further include applying the adhesion promoter composition onto the surface of the thermoplastic composite. In an embodiment, the reactive silane forms a chemical reaction with the surface, the primer, or the surface coating. The application method may include spraying, brushing, dipping, rolling, wiping, or combinations thereof, in addition to other known application methods known to those skilled in the art. In certain embodiments, grit blasting or other surface preparation techniques may be used.The adhesion promoter composition comprises one or more reactive silanes having the general formula ((RO)n-SiY)m-(CH2)xA, where n=2-3, m=1-2, Y is absent (when n=3) or is a C1-C6 alkyl group, x=1-8, A=none, NHz, SH, or epoxy, z=1-2, and R=C1-C6 alkyl, one or more swelling agents, and one or more organic solvents, where the one or more reactive silanes form a complex with the one or more swelling agents through hydrogen and / or ionic bonds.

[0060]

[0063] Additional steps of the method for applying the adhesion promoter composition may include heating or abrading the thermoplastic material or the surface of the thermoplastic composite, such as heat curing the adhesion promoter at a temperature of about 50° C. to about 200° C. for about 1 minute to about 120 minutes, or abrading the surface of the thermoplastic composite before applying the adhesion promoter composition onto the surface of the thermoplastic composite. The method of treating a surface with the adhesion promoter composition may include one or more heating methods. Heating methods include, but are not limited to, ambient heating or evaporation, convection heating, infrared radiation heating, induction heating, or combinations thereof. In an embodiment, the method may include a step of pausing, waiting, dwelling, or allowing the composite treated with the adhesion promoter composition to evaporate or release the solvent at ambient conditions prior to the heating step at elevated temperature. Such an evaporation step may be performed using a heat gun or infrared lamp, or any of the heating methods disclosed herein. In embodiments, heat curing may be carried out at a temperature of 120° C. for 30 minutes, or between 1 minute and about 60 minutes, or between about 5 minutes and about 45 minutes, or between about 10 minutes and 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.

[0061]

[0064] Surfaces or substrates used for application of the adhesion promoter include, but are not limited to, aluminum, titanium, carbon fiber composites, carbon fiber reinforced composites, fiberglass composites, thermoplastic materials, thermoset materials, or combinations thereof. For example, the surface may be a surface of a bridge truss, a support, a building, a vehicle such as an atmospheric vehicle, an aerospace vehicle, an unmanned vehicle, an aircraft, a spacecraft, a satellite, a rocket, a missile, or the like, or a component thereof. In an exemplary embodiment, the polymer formulation layer in the method of applying the adhesion promoter composition may include an epoxy-based polymer formulation, a polyurethane-based polymer formulation, a polysulfide-based polymer formulation, a polyaryletherketone (PAEK), such as polyetheretherketone (PEEK), polyetherketoneketone (PEKK), or a combination thereof. The adhesion promoter composition may be stored inertly, at room temperature, in a refrigerator, in a freezer, or a combination thereof. In certain embodiments, the adhesion promoter composition may be allowed to return to room temperature before mixing or use. In certain aspects, the substrate or surface can be prepared with an optional degreasing solvent wipe prior to application of the adhesion promoter, which can then be applied to the substrate by spray, brush, roller, wipe, wipe-on / wipe-off, pouring, or combinations thereof.

[0062]

[0065] The method of applying the adhesion promoter composition may include separating one or more particles and / or relatively large adhesion promoter agglomerates from the adhesion promoter composition after homogenization or mixing. For example, the method may include separating the particles and / or relatively large adhesion promoter agglomerates from the adhesion promoter composition via filtration. The filtration may include passing the adhesion promoter composition including one or more particles (e.g., glass particles) and / or relatively large adhesion promoter agglomerates 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.

[0063]

[0066] A method for utilizing the adhesion promoter composition to treat a surface may include applying or contacting the adhesion promoter composition to a surface. The adhesion promoter composition may be contacted to the surface via a brush, gauze, roller, syringe, extrusion gun, spray gun, or the like, or any combination thereof. The adhesion promoter composition may be applied using a Sempen® Applicator available from PPG Industries, Inc. (Sylmar, Calif.). The adhesion promoter composition may be configured to omit one or more steps in a conventional process or method of preparing a surface for application of a sealant, surface treatment, surface coating, or the like. For example, in a conventional process of preparing a surface for application of a sealant, adhesive, surface treatment, or surface coating, the surface is first treated with a solvent and then treated with an adhesion promoter or an adhesion promoter film is formed.

[0064] Working Example

[0067] Although exemplary examples of adhesion promoter compositions are described with reference to the accompanying tables, it should be noted that alternative compositions, ratios of ingredients, or specific ingredients as conveyed in the present teachings may be used in the adhesion promoter compositions and applications as described herein.

[0065]

[0068] MaterialSwelling solvents or compounds including 4-chloro-1-naphthol (CNO), 4-chlorophenol (CPhO) were purchased from Aldrich. 2,2'-methylene bis(4-chlorophenol) (BCPhO) was purchased from TCI. Solvents including propylene glycol propyl ether (PnP), dipropylene glycol dimethyl ether (DMM) were obtained from Aldrich. Methyl isobutyl ketone (MIBK) was purchased from Sydney Solvent (commercial grade, 20 L) and isopropanol was purchased from Merck. 3-aminopropyltriethoxysilane (APS), 3-aminopropyltrimethoxysilane (APTMS), 3-aminopropylmethyldimethoxysilane (APMDMS) were all products of Aldrich. PAEK composites such as carbon fiber reinforced PEEK, glass fiber reinforced PEKK, or carbon fiber reinforced PEKK were also used. Organic solvent primers, BMS10-103 Gr A, 45GY005 Chrome-Free Water Reducible Epoxy Primer, and BMS10-60 Desothane topcoat (CA8000 / B70846 / CA8000B) were purchased from PPG.

[0066]

[0069] Preparation of diffusion coupling solution (3.5% APMDES / BCPhO=0.375 solution as an example): Generally, the solutions were prepared in three steps. Step 1 involved the preparation of a mixed solvent of 50% MIBK, 20% DMM, and 30% PnP. 500g MIBK, 300g PnP, and 200g DMM were weighed into a 1.5L bottle. The mixture was magnetically stirred at 250 rpm for 5 minutes to form a clear, transparent solution. Step 2 involved the preparation of a BCPhO solution. In a 1.5L Schott bottle with a lid, 23g BCPhO was added, followed by 965g of the mixed solvent. The mixture was magnetically stirred at 250 rpm for 5 minutes to obtain a clear, yellow solution. Step 3 involved the preparation of an adhesion promoter spray solution (AP). 12g APMDES was added to the solution from step 2. The solution was magnetically stirred at 250 rpm for 10 minutes. After standing at room temperature for 1 hour, the solution was ready for spraying / application. The preparative procedures are for illustrative purposes and may include alternative or supplemental methods or materials as disclosed in the present teachings.

[0067]

[0070] Application of Adhesion Promoter Diffusion Coupling Solution:Sanded or unsanded BMS8-422, BMS8-429, or BMS8-399 composites were cleaned by wiping several times with IPA. The solution was sprayed onto the samples using a high volume low pressure (HVLP) sprayer. The coatings were allowed to dry in air for 30 minutes and then heated at 120°C for 30 minutes.

[0068]

[0071] Preparation of sealant and adhesive samples : Composite samples were cut to 25 × 100 mm using a diamond saw from composite panels supplied by Boeing. Cotton cloth or coated glass fiber mesh was used as the release medium. One end of the composite coupon was covered with 18 mm wide 3M Scotch tape to facilitate the creation of a peel area on the composite surface for peel testing. Freshly prepared sealant was applied to both the PEEK composite surface and the release medium (both surfaces), taking care to ensure complete wetting of the sealant in the test area. The release medium and composite coupon were then placed in a home-made sample holder and secured with metal clamps. Excess sealant was squeezed out of the running channels to obtain a sealant thickness of 3.1 mm between the composite and the release medium. The two-part sealant was mixed immediately before application according to the manufacturer's instructions. The assembly was cured at room temperature for 14 days.

[0069]

[0072] Preparation of coated and bonded samples: The composite panels were cleaned with IPA and wiped with AC12165 DuPont Aerospace wipes BMS 15-5F before and after sanding. To achieve a uniform, matte finish, a combination of pneumatic orbital sanding and hand sanding was used, followed by sanding with Flexovit 180 grit aluminum oxide sandpaper for approximately 1 minute. The sandpaper was changed after every two samples were sanded. Spray coating was performed using a MACH 1A HVLP Automatic Spray gun equipped with a 1.4 mm fluid nozzle and a 94P cap. The inlet pressure was set at 40 PSI. For coatings according to configuration I, only the primer was used in the coating stack as shown in Table 1. For the remaining samples, the primer and topcoat were used after surface preparation as shown in configuration II in Table 1. TIFF2025000574000001.tif87170Table 1: Examples of coatings on PEEK thermoplastic composites

[0070]

[0073] Two crosscoats of BMS10-103 Gr A primer were applied to the composite panels as specified in Table 1 to achieve a film thickness of about 0.5 to about 0.8 mils. The panels were allowed to dry at ambient temperature for about 2 to about 2.5 hours before topcoat application. The topcoat was thoroughly mixed before application. BMS10-60 Desothane topcoat (CA8000 / B70846 / CA8000B) was spray applied onto the composite panels to achieve a film thickness of 2 to 3 mils and cured at 24±5°C and 30-60% RH for 14 days before testing. For primer-only coatings (Configuration 1), the thickness of the primer is approximately twice the thickness of the primer used in Configuration II (primer+topcoat coating).

[0071]

[0074] Peel strength test: Quantitative adhesion was evaluated using the peel strength adhesion rating detailed in BSS7257, based on ASTM D3330. The minimum adhesion required to pass is a peel strength of 20 pounds per inch of width with a minimum of 95% cohesive failure as the adhesive failure mode. The adhesion value and failure mode were recorded for each sample. Adhesion was measured after the sealant was allowed to dry cure for 14 days ("dry adhesion") and after immersion in jet fuel or a 3% NaCl solution for 7 days.

[0072]

[0075] Scribe adhesion : Scribe bonding was performed generally in accordance with BOEING specification supporting standard BSS7225. The test specimen was scribed with a sharp blade to cut through the coating and score the base substrate with five parallel scores, repeated at a 45 degree angle to create a crosshatch pattern. The parallel scores were 0.12 inches apart. A piece of masking tape, Tape 250 (3M Company), was used to apply to the 45 degree intersections of the crosshatch patterns and held down firmly using a roll of tape. The tape was then quickly but smoothly removed perpendicular to the panel and inspected for removal of the coating from the substrate and rated according to the standard criteria. A rating of 8 or greater is considered a pass.

[0073]

[0076] SIJA Adhesion Testing: Adhesion testing was performed generally in accordance with BSS 7391 using a Single Impact Jet Apparatus (SIJA, Cambridge). The initial setup was configured with a 1m nozzle, using 0.22 calibre 5.5mm Crosman Accupell Pointed Pellets (#11246). The nozzle to specimen distance was fixed at 7mm. Testing was completed after overnight immersion in water, using a 45° specimen to impact drop geometry, with impact location identified using a line laser. Each location was impacted once by the water jet, with the pressure of the "shot" displayed below the impact testing adhesion. A target speed of 600m / s was used for each individual shot. GIMP software was used to assess the area of ​​removal. A paint removal area of ​​<5mm was assessed. 2 The above cases were considered as passing.

[0074]

[0077] FIG. 4 illustrates the results of an exemplary adhesion test according to the present disclosure. As briefly described above, adhesion evaluation was performed using a Single Impact Jet Apparatus (SIJA, Cambridge). The initial setup was configured using a 1.0 mm nozzle, using 0.22 caliber 5.5 mm Crosman Accupell Pointed Pellets (#11246). Testing was completed after a minimum of 20 hours of immersion in water, using a 45° specimen to impact target geometry, with a line laser used to identify impact locations. Adhesion was tested using one water jet at each location, with the pressure of the "shot" displayed below the impact. The speed of each individual shot was recorded for future reference, but generally the speed was approximately 600 m / s (± 25 m / s). GIMP software was used to evaluate the removal area. Paint removal areas <5 mm were evaluated using the GIMP software. 2 A pass was considered when the area was calculated. Two methods were used to calculate the area. 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) was considered when the area was calculated. 2 ) is shown in image 402.

[0075]

[0078] Rain erosion test Rain erosion testing was performed in accordance with BOEING specification supporting standard BSS7393. The leading edge of the composite foil exposed to raindrops was generated by taping 1.82 ± 0.03 in. from the bottom edge of the foil with PG-777 tape (3M Company) after surface preparation and before application of the topcoat. After curing, the foil was submerged in water for 16-24 hours, then loaded into a rotating arm chamber and rotated at an average speed of 385 mph, exposing it to simulated rain with a rainfall rate of 3-4 in. per hour and droplet size of 1-4 mm for approximately 30 minutes. The specimens were then removed and analyzed.

[0076]

[0079] Skydrol Hydraulic Fluid Test : 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 scribe adhesion testing.

[0077]

[0080] The results of various tests of the adhesion promoter compositions are summarized in the following tables. Any deviations or modifications from the standard procedures are explained with reference to each table.

[0078]

[0081] Example 1. In this example, sanded BMS8-422 was sprayed with treatment solutions containing only aminosilane or swelling agents. The solvents used in these formulations included 20% DMM, 30% PnP, and 50% MIBK. After drying at room temperature for 30 minutes, the specimens were cured at 120°C for 30 minutes. Primers and topcoats were sprayed onto the specimens according to the methods described above. It can be seen that the dry scribe adhesion is all better than the sanded only (no adhesion promoter) samples. However, after 30 days of condensed humidity at 49°C, the scribe adhesion results were rated <7. These results indicate that the use of silane or swelling agents alone is insufficient to improve adhesion of the coating surface finish. TIFF2025000574000002.tif93170Table 2. Scribe adhesion performance when diffusion linking adhesion promoters containing aminosilane or expansion agent only were applied over sanded BMS8-422 and coated with primer and topcoat.

[0079]

[0082] Example 2. Adhesion was tested on sanded BMS8-422 using mixtures of CNO and aminosilanes with different methoxy or ethoxy silyl groups. The molar ratio of aminosilane to CNO was 1:1. The solvent used in these formulations included 20% DMM, 30% PnP, and 50% MIBK. The specimens were air dried for 30 minutes and then cured in an oven at 120°C for 30 minutes. All formulations except 3-aminopropyldimethylethoxysilane, monoethoxy, gave better scribe and SIJA adhesion results than sanding alone. Results showed that the presence of two or more alkoxy groups in the silane and the combination of swelling agent and silane are important. TIFF2025000574000003.tif93170Table 3. Scribe and SIJA adhesion of diffusion-linked adhesion promoter formulations containing mixtures of CNO and aminosilane.

[0080]

[0083] Example 3. In the following example, BMS8-399 with and without sanding was sprayed with 3.5% APMDES / BCPhO with 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 at temperatures of 100, 120, and 150°C for 30 minutes. For samples with sanding and adhesion promoter added, adhesion passed at all temperatures. However, for the no sanding + adhesion promoter condition, condensation humidity scribe adhesion was observed to fail at the higher temperature of 150°C. TIFF2025000574000004.tif67170Table 4. Scribe and SIJA adhesion of diffusion-linked adhesion promoter formulation (3.5% AMPDES / BCPhO solution, AMPDES:BCPhO ratio 1:2) to BMS8-399 (with and without sanding) at different temperatures.

[0081]

[0084] Example 4. The examples summarized in Table 5 used adhesion promoter compositions based on 3.5% solutions based on active ingredients (total silane and swelling agent). These examples were cured at 120°C for 30 minutes. The solvents used in these formulations were 20% DMM, 30% PnP, 50% MIBK and two passes were used. The results summarized in Table 5 suggest that a range of silane:swelling agent ratios will result in sufficient adhesion improvement. TIFF2025000574000005.tif129170 Table 5: Scribe and SIJA adhesion of diffusion-linked adhesion promoter formulations with various ratios of silane:swelling agent

[0082]

[0085] Example 5. In the examples summarized in Table 6, the silane to swelling agent ratio was 0.5:1 for all compositions 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 APS (aminopropyltriethoxylsilane) to the APMDES / BCPhO formulations resulted in a slight improvement in the condensation humidity adhesion rating. The ratio of APS to APMDES did not significantly affect the adhesion results. TIFF2025000574000006.tif142170 Table 6: Scribe and SIJA adhesion of diffusion-linked adhesion promoter formulations with mixed silanes

[0083]

[0086] Example 6. Table 7 shows examples using a water-based 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 adhesion promoter compositions marked with an asterisk (*), 20% APS was added to the adhesion promoter composition based on the amount of APMDES. The treatments summarized in Table 7 provided good scribe and SIJA adhesion when using a water-based primer. The results in Table 7 demonstrated that there was no significant difference between 2 passes and 4 passes (i.e., different adhesion promoter thicknesses). TIFF2025000574000007.tif174170Table 7: Scribe and SIJA adhesion of 3.5% APMDES / BCPhO formulation using water-based primer (45GY005 Chrome-Free Water Reducible Epoxy Primer) as surface finish

[0084]

[0087] Example 7. In these examples in Table 8, glass fiber reinforced PEKK composite BMS8-429 was used as substrate. Adhesion promoter solutions of varying concentration, ratio of aminosilane to swelling agent, and presence or absence of APS (the amount of APS is 20% of APMDES) were sprayed onto the surface. After air drying for 30 minutes, the specimens were cured in an oven at 120°C for 30 minutes. Subsequently, organic solvent primer BMS10-103 Gr.A and BMS10-60 Desothane topcoat (CA8000 / B70846 / CA8000B) were applied. After 2 weeks of curing at room temperature, scribe adhesion and SIJA were tested. All treatments gave good results. All formulations improved adhesion, demonstrating that the adhesion promoter formulations lead to improved adhesion of glass fiber reinforced PEKK. TIFF2025000574000008.tif157170 Table 8. Adhesion results of adhesion promoter formulations to glass fiber PEKK composite BMS8-429

[0085]

[0088] Example 8. In the examples shown in Table 9, BMS8-399 flat panels and rain eroded foils were coated with various aminosilanes and swelling agents at different concentrations and ratios and overcoated with either 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 improved the scribe and SIJA adhesion and also passed the rain erosion rating (8 or higher) of the sanded, post-treated, and painted composites. TIFF2025000574000009.tif147170Table 9. Scribe and SIJA adhesion, Skydrol pencil hardness, and rain erosion results for selected adhesion promoter solutions.

[0086]

[0089] Example 9. In the example with results in Table 10, all adhesion promoter solutions had 5% solids and APMDES / BCPhO=0.375, but different solvent systems were used. The AP solutions were sprayed onto an unsanded BMS-399 surface. After the solvent was dried at RT for 30 min, the AP layer was further cured in an oven at 120° C. for 30 min. Then, primer and topcoat were applied under typical conditions. SIJA adhesion performance was <5mm 2 The test was passed with a peel area of ​​10. Scribe adhesion both dry and after 7 days of water immersion was above 8, with most scoring 10. However, after 30 days of condensed humidity testing, the single and dual solvent systems failed with ratings of 5 to 7. This example also shows that solvents other than MIBK and PnP also work, especially in solvent combinations. TIFF2025000574000010.tif85170 Table 10: Scribe and SIJA adhesion of 5% based adhesion promoter formulations with APMDES / BCPhO=0.375 ratio but different carrier solvents

[0087]

[0090] Example 10: In these examples in Table 11, 5% APS-CNO or APS-CPO solutions with 1:1 ratio of silane to swelling agent in mixed solvent were sprayed onto the BMS8-422 surface. After drying in air for 60 minutes, the samples were cured at 120°C for 30 minutes. PR-1776M Class B low weight fuel tank sealant was applied and the assemblies were cured at RT for 14 days. Without the application of adhesion promoter, no adhesion between the sealant and the PEEK BMS8-422 was observed on both sanded and unsanded specimens. Application of adhesion promoter and thermal cure significantly increased the adhesion between the sealant and the PEEK (failure occurred within the sealant, not between the sealant and the composite). All samples treated with adhesion promoter solution also passed salt and jet fuel immersion at 160°F for 7 days. TIFF2025000574000011.tif62170Table 11. Peel adhesion results of sealants on BMS8-422 after application of adhesion promoter and the effect of immersion in salt solutions and jet fuel. Note: AF: adhesive failure; CF: cohesive failure

[0088]

[0091] Although the present teachings have been illustrated with respect to one or more embodiments, changes and / or modifications can be made to the illustrated examples without departing from the spirit and scope of the appended claims. For example, while a process is described as a sequence of acts or events, it will be understood that the present teachings are not limited by the order of such acts or events. Some acts may occur in different orders and / or may occur simultaneously with other acts or events than those described herein. Furthermore, not all process steps may be required to implement a methodology in accordance with one or more aspects or embodiments of the present teachings. It will be understood that structures and / or process steps may be added, or existing structures and / or process steps may be removed or modified. Furthermore, one or more of the acts described herein may be performed in one or more other acts and / or phases. Still further, to the extent that "including," "includes," "having," "has," "with," or variations thereof are used in any of the detailed description and claims, these terms are intended to be as inclusive as the term "comprising." The phrase "at least one of" is used to mean that one or more of the listed items may be selected. Furthermore, in the description and claims herein, the term "on" as used in relation to two materials, i.e., one "on" the other, means that there is at least some contact between the materials, whereas "over" means that the materials are in close proximity, possibly with one or more additional intervening materials, such that contact is possible but not required. Neither "on" nor "over" as used herein implies any directionality. The term "conformal" describes a coating material in which the angles of the underlying material are protected by the conformal material.The term "about" indicates that some variation may be made to the recited value without causing incompatibility of the process or structure to the illustrated embodiment. The terms "couple," "coupled," "connect," "connection," "connected," "in connection with," and "connecting" mean "in connection with" or "in connection with via one or more intermediate elements or members." Finally, "exemplary" or "illustrative" indicates that the description is used as an example, rather than implying ideality. Other embodiments of the present teachings will be apparent to those skilled in the art from consideration of the specification and practice of the present disclosure. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the present teachings being indicated by the following claims.

Claims

1. 1. An adhesion promoter composition comprising: one or more reactive silanes having the general formula ((RO)n-SiY)m-(CH2)x-A, where n=2-3, m=1-2, Y is absent (when n=3) or is a C1-C6 alkyl group, x=1-8, A=none, Hz, SH, or epoxy, z=1-2, and R=C1-C6 alkyl; one or more swelling agents; one or more organic solvents; Including, The one or more reactive silanes form a complex (208) with the one or more swelling agents by hydrogen bonding and / or ionic bonding; Adhesion promoter composition.

2. 10. The adhesion promoter composition of 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. 10. The adhesion promoter composition of claim 1, wherein the one or more reactive silanes comprise amine-functional groups, epoxy-functional groups, mercapto-functional groups, isocyanate-functional groups, or combinations thereof.

4. 2. The adhesion promoter composition of claim 1, wherein the one or more reactive silanes comprise trialkoxysilanes such as trimethoxy, triethoxy, tripropoxy, or dialkoxysilanes such as dimethoxy, diethoxy, dipropoxy, monoalkoxysilanes such as dimethylmethoxy, dimethylethoxy, diethylmethoxy, diethylethoxy, or combinations thereof.

5. 10. The adhesion promoter composition of claim 1, wherein the one or more reactive silanes comprises a multialkoxysilane.

6. 6. The adhesion promoter composition of claim 5, wherein the one or more reactive silanes comprise bis-trimethoxysilane, bis-triethoxysilane, tris-trimethoxysilane, tris-triethoxysilane, or combinations thereof.

7. The one or more reactive silanes may be 3-aminopropyltrimethoxysilane (APTMS), 3-aminopropyltriethoxysilane (APTES), 3-aminopropylmethyldimethoxysilane (APMDMS), 3-aminopropylmethyldiethoxysilane (APMDES), 3-aminopropyldimethylethoxysilane (APDMES), 3-(2-aminoethylamino)propyltrimethoxysilane (AEPTMS), 3-(2-aminoethylamino)propyltriethoxy 2. The adhesion promoter composition of claim 1, wherein the adhesion promoter composition is selected from the group consisting of 3-(2-aminoethylamino)propyl dimethoxymethyl silane (AEDMMS), 3-(2-aminoethylamino)propyl diethoxymethyl silane (AEDMES), 3-[2-(2-aminoethylamino)ethylamino]propyl trimethoxy silane (TMSDETA), and 3-[2-(2-aminoethylamino)ethylamino]propyl triethoxy silane (TESDETA).

8. 2. The method of claim 1, 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).

9. 2. The adhesion promoter composition of claim 1, wherein the other functional silane comprises (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 combinations thereof.

10. 10. The adhesion promoter composition of claim 1, 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.

11. 10. The adhesion promoter composition of claim 1, wherein the one or more swelling agents are present in the adhesion promoter composition in an amount of from 1 wt% to 10 wt%, based on the total weight of the adhesion promoter composition.

12. The one or more swelling agents may be 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 (DCPO), 2- ...

2. The adhesion promoter composition of claim 1, wherein the phenol or naphthol derivative, in particular a chloro-substituted phenol or naphthol derivative, is selected from the group consisting of phenol or naphthol derivatives, in particular chloro-substituted phenol or naphthol derivatives, such as 3,3'-dichloro-[1,1'-binaphthalene]-2,2'-diol, 2,2'-methylenebis(4-chlorophenol) (BCPhO), 4,4'-isopropylidenebis(o-chlorophenol), and 2,6-bis(2-hydroxy-5-chlorobenzyl)-4-chlorophenol.

13. 2. The adhesion promoter composition of claim 1, wherein the one or more organic solvents comprise an alcohol, an ether, an ester, a ketone, such as isopropanol, butyl alcohol, di(propylene glycol) peach methyl ether (DPM), dipropylene glycol dimethyl ether (DMM), propylene glycol monopropyl ether (PnP), dimethyl isosorbide, propylene glycol monomethyl ether acetate (MPA), butyl acetate, pentyl acetate, ethylene glycol diacetate, propylene glycol diacetate, methyl isobutyl ketone (MIBK), methyl amyl ketone (MAK), or a combination thereof.

14. 1. An adhesion promoter composition comprising: one or more reactive silanes having the general formula ((RO)n-SiY)m-(CH2)x-A, where n=2-3, m=1-2, Y is absent (when n=3) or is a C1-C6 alkyl group, x=1-8, A=none, Hz, SH, or epoxy, z=1-2, and R=C1-C6 alkyl; one or more swelling agents; one or more organic solvents; Including, one or more reactive silanes form complexes (208) with one or more swelling agents through hydrogen and / or ionic bonding; the molar ratio of the reactive silane(s) to the swelling agent(s) is from about 0.1:1 to about 1.5:1; Adhesion promoter composition.

15. A composite part, a thermoplastic or thermoset composite; 1. An adhesion promoter composition disposed on a surface of a thermoplastic composite, comprising: one or more reactive silanes, and One or more swelling agents Including, one or more reactive silanes form complexes (208) with one or more swelling agents through hydrogen and / or ionic bonding; The adhesion promoter composition diffuses into at least a portion of the thermoplastic composite; an adhesion promoter composition; a surface coating disposed on the surface of the thermoplastic composite having the adhesion promoter disposed thereon; Composite parts, including:

16. The composite part of claim 15 , wherein the one or more reactive silanes are capable of forming a chemical reaction (210) with the surface coating.

17. 16. The composite part of claim 15, wherein the thermoplastic composite comprises polyaryletherketone (PAEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), polyetherimide (PEI), polyimide, or combinations thereof.

18. 16. The composite part of claim 15, wherein the surface coating comprises an epoxy-based polymer formulation, a polyurethane-based polymer formulation, a polysulfide-based polymer formulation, or a combination thereof.

19. 16. The composite part of claim 15, 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).

20. 16. The composite part of claim 15, 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).

21. 16. The composite part of claim 15, 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 combinations thereof.

22. 16. The composite part of claim 15, 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).

23. The one or more swelling agents may be 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 (CNO), 2,4-dichloro-1-naphthol ( 16. The composite part according to claim 15, wherein the phenol or naphthol derivative, in particular a chloro-substituted phenol or naphthol derivative, is selected from the group consisting of phenol or naphthol derivatives, in particular chloro-substituted phenol or naphthol derivatives, such as 3,3'-dichloro-[1,1'-binaphthalene]-2,2'-diol, 2,2'-methylenebis(4-chlorophenol) (BCPhO), 4,4'-isopropylidenebis(o-chlorophenol) and 2,6-bis(2-hydroxy-5-chlorobenzyl)-4-chlorophenol.

24. 16. The composite part of claim 15, 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.

25. A method for applying an adhesion promoter composition (300, 302, 306), comprising: contacting the reaction (210) product of claim 1 on a surface of a thermoplastic composite (304) to form a film; Heating the membrane; and forming an adhesion promoter film of less than 2 microns; applying a surface coating over the adhesion promoter composition; A method comprising:

26. 26. The method for applying the adhesion promoter composition (300, 302, 306) of claim 25, wherein the thermoplastic composite comprises polyaryletherketone (PAEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), polyetherimide (PEI), polyimide, or combinations thereof.

27. 26. The method for applying the adhesion promoter composition (300, 302, 306) of claim 25, wherein the surface coating comprises an epoxy-based polymer formulation, a polyurethane-based polymer formulation, a polysulfide-based polymer formulation, or a combination thereof.

28. 26. The method for applying the adhesion promoter composition (300, 302, 306) of claim 25, 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).

29. 26. A method for applying the adhesion promoter composition (300, 302, 306) of claim 25, 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).

30. 26. The method for applying the adhesion promoter composition (300, 302, 306) of claim 25, wherein the other functional silanes comprise (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 combinations thereof.

31. 26. The method for applying the adhesion promoter composition (300, 302, 306) of claim 25, 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).

32. The swelling agent or agents may be selected from the group consisting of phenol or naphthol derivatives, chloro-substituted phenol or naphthol derivatives, 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 ...

26. A method for applying the adhesion promoter composition (300, 302, 306) of claim 25, wherein the adhesion promoter is selected from the group consisting of 3,3'-dichloro-[1,1'-binaphthalene]-2,2'-diol, 2,2'-methylenebis(4-chlorophenol) (BCPhO), 4,4'-isopropylidenebis(o-chlorophenol), and 2,6-bis(2-hydroxy-5-chlorobenzyl)-4-chlorophenol.

33. 26. The method for applying the adhesion promoter composition (300, 302, 306) of claim 25, wherein the one or more organic solvents comprise alcohols, ethers, esters, ketones, isopropanol, butyl alcohol, di(propylene glycol) peach methyl ether (DPM), dipropylene glycol dimethyl ether (DMM), propylene glycol monopropyl ether (PnP), dimethyl isosorbide, propylene glycol monomethyl ether acetate (MPA), butyl acetate, pentyl acetate, ethylene glycol diacetate, propylene glycol diacetate, methyl isobutyl ketone (MIBK), methyl amyl ketone (MAK), or combinations thereof.

34. 26. A method for applying an adhesion promoter composition (300, 302, 306) as described in claim 25, wherein applying the adhesion promoter composition onto a surface of a thermoplastic composite further comprises applying the adhesion promoter composition onto a surface of a thermoplastic composite.

35. 26. A method for applying the adhesion promoter composition (300, 302, 306) of claim 25, further comprising heat curing the adhesion promoter at a temperature of about 10°C to about 200°C for a period of about 1 minute to about 120 minutes.

36. 30. A method for applying the adhesion promoter composition (300, 302, 306) of claim 26, further comprising abrading the surface of the thermoplastic composite prior to applying the adhesion promoter composition onto the surface of the thermoplastic composite.

37. 26. A method for applying an adhesion promoter composition (300, 302, 306) according to claim 25, wherein the adhesion promoter film is less than 1 micron.

38. 26. The method for applying an adhesion promoter composition (300, 302, 306) according to claim 25, wherein the adhesion promoter film is from about 100 nm to about 800 nm.

39. 26. The method for applying the adhesion promoter composition (300, 302, 306) of claim 25, wherein the surface coating comprises one of an epoxy coating, a polyurethane coating, a sealant, or an adhesive.

Images