Conductive polymer coating composition and method of making the same

Abstract

To provide a polymer coating composition which can inhibit functional additives from settling or segregating in a production or coating process and / or maintain a percolation threshold to maintain the electrical and / or thermal conductivity.SOLUTION: A conductive polymer coating composition (10) includes a conductive fibrillated structure (150) and a base polymer (250). The conductive fibrillated structure (150) includes a fibrillated polymer (100) and a conductive polymer (200) grafted on the fibrillated polymer (100). The conductive polymer coating composition (10) has an electrical conductivity from about 10-5 S / cm to about 10+1 S / cm and a thermal conductivity from about 1.1 W / m K to about 3 W / m K.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] FIELD OF THE DISCLOSURE The present disclosure relates generally to polymeric coating compositions, and more particularly to conductive polymeric coating compositions and methods for making the same. [Background technology]

[0002] Polymer coating compositions are used in various industries to add functionality to substrates through coatings. These functionalities include weather resistance, corrosion protection, aesthetic design and coloring, impact resistance, and the like. For example, in the aviation industry, polymer coating compositions can be used on composite or metal substrates to improve thermal and electrical conductivity in addition to the usual requirements for corrosion protection, weather resistance, aesthetics, and the like. For example, polymer coatings can be used on aircraft surfaces where static electricity accumulates. Conductive coatings can prevent this type of charge buildup and protect electronic devices from strong electric fields.

[0003] The functionality of polymer coating compositions can generally be achieved by incorporating particulate matter into the polymer coating composition. For example, adding metal particles and pigments to a polymer coating composition can increase the conductivity of the polymer coating composition and form continuous pathways for thermal and electrical conduction. However, a major drawback of such systems is that the desired functionality is lost if the particulate matter separates during various stages of the coating process, such as preparation, application, or curing. In addition, environmental factors such as temperature, pressure, and humidity during use can also impair functionality. That is, the functional performance of a polymer coating composition is affected by the degree of particulate matter settling or separation that occurs during the formation or coating process of the polymer coating composition. For example, the separation of conductive particulate matter in a polymer coating composition can disrupt the percolation effect and result in a loss of conductivity.

[0004] Therefore, there is a need for polymer coating compositions that can inhibit settling or separation of functional additives during the formation or coating process and / or maintain a percolation threshold to maintain electrical and / or thermal conductivity. Summary of the Invention

[0005] This summary is intended to provide a simplified overview of some aspects of one or more embodiments of the present disclosure. It is not intended to be exhaustive, to identify key or critical elements of the present teachings, or to delineate the scope of the present disclosure. Its sole purpose is to present one or more concepts in a simplified form as a prelude to the more detailed description that is presented later.

[0006] The above and / or other aspects and utilities exemplified in the present disclosure are achieved by providing a conductive polymer composition comprising a conductive fibrillated structure and a base polymer, the conductive fibrillated structure comprising a fibrillated polymer and a conductive polymer grafted to the fibrillated polymer, the conductive polymer coating composition having a viscosity of about 1000 psig. -5 S / cm to about 10 +1 It has an electrical conductivity of about 1.1 W / m·K to about 3 W / m·K.

[0007] The composition can include about 1 wt % to about 25 wt % of the conductive fibrillated structure, about 20 wt % to about 90 wt % of a base polymer, about 0.5 wt % to about 20 wt % of the fibrillated polymer, and about 0.1 wt % to about 15 wt % of the conductive polymer, wherein the base polymer includes one or more of epoxy, acrylic, polyurethane, polysiloxane, polycarbonate, polysilazane, styrene-butadiene rubber, styrene block copolymer, acetonitrile butadiene styrene, polyamide, polyether ketone, polyethylene terephthalate, derivatives thereof, or combinations thereof.

[0008] The fibrillating polymer may include one or more of polytetrafluoroethylene (PTFE), sulfonated tetrafluoroethylene-based fluoropolymer copolymers such as Nafion, nylon, cellulose, high density polyethylene (HDPE), or combinations thereof.

[0009] The conductive polymer can include one or more of polyaniline, polypyrrole, poly(N-methylpyrrole), poly(N-ethylpyrrole), poly(N-propylpyrrole), poly(N-butylpyrrole), poly(3,4-ethylenedioxythiophene), poly(p-phenylenevinylene), 3,4-propylenedioxypyrrole, poly(p-phenylenevinylene), 3,4-propylenedioxypyrrole, 3,4-propylenedioxythiophene, polyfuran, derivatives and copolymers thereof, or combinations thereof.

[0010] The conductive polymer coating composition may further comprise about 0.1 wt % to about 10 wt % of one or more conductive additives, wherein the one or more conductive additives may include a carbonaceous material, a conductive pigment, a metal particle, polyaniline, polypyrrole poly(3,4-ethylenedioxythiophene), an aluminosilicate, boron nitride, aluminum nitride, a nitride, a carbide, a polybenzoxazine, or a combination thereof.

[0011] The conductive fibrillated structure may further comprise from about 0.1% to about 10% by weight of the one or more conductive additives.

[0012] The conductive polymer is a composite conductive polymer that includes one or more conductive additives.

[0013] The composition can further include about 15% to about 40% by weight of a solvent, which can include one or more of hexane, acetone, N-methyl-2-pyrrolidone, xylene, water, methyl ethyl ketone, dimethylacetamide, cymene, toluene, cyclohexane, α- and β-pinene, hexafluoroisopropanol, dimethylformamide, dimethyl sulfoxide, or combinations thereof.

[0014] The solvent consists essentially of water.

[0015] The conductive fibrillated structure can form a reinforcing phase through the base polymer.

[0016] The conductive polymer coating composition may have a hardness measured as H or greater in a pencil hardness test according to ASTM D3363.

[0017] The conductive polymer coating composition may have a peel adhesion strength measured in accordance with ASTM D4541 of about 12 to about 20 MPa.

[0018] The conductive polymer coating composition may have an impact toughness measured at 7 Joules or greater when tested according to ASTM D2794.

[0019] The conductive polymer coating composition may have a corrosion resistance measured in a salt spray test according to ASTM B117 of greater than or equal to 3000 hours.

[0020] The above and / or other aspects and utilities exemplified in the present disclosure can also be achieved by providing a conductive object comprising the conductive polymer composition described above, wherein a continuous conductive network is formed in an area where the conductive polymer coating composition is applied.

[0021] The conductive polymer coating composition may have an optical transparency of from about 65% to about 95%.

[0022] The above and / or other aspects and utilities exemplified in the present disclosure are also achieved by providing a method for producing a conductive polymer composition, the method comprising: forming a conductive fibrillated structure; forming a base polymer; and mixing the base polymer with the conductive fibrillated structure.

[0023] Producing a conductive fibrillated structure can include fibrillating a fibrillizable polymer, producing a conductive polymer, and grafting the conductive polymer onto the fibrillated polymer.

[0024] Fibrillating the fibrillizable polymer can include one or more of solvent crazing the fibrillizable polymer, shearing the fibrillizable polymer, electrospinning the fibrillizable polymer, biaxially stretching the fibrillizable polymer, wet-, dry-, and melt-spinning the fibrillizable polymer, or combinations thereof.

[0025] Grafting the conductive polymer onto the fibrillating polymer can include one or more of in-situ polymerization of the conductive polymer and the fibrillating polymer, fibril surface functionalization of the fibrillating polymer with the conductive polymer, fibril surface modification of the fibrillating polymer with the conductive polymer, or combinations thereof.

[0026] The above and / or other aspects and utilities embodied in the present disclosure may be substantially achieved by providing a conductive polymer composition as described above with reference to the examples, excluding comparative examples, if any.

[0027] Further fields of application will become apparent from the detailed description provided below. It should be noted that the detailed description and specific examples, while indicating preferred embodiments of the present disclosure, are intended for purposes of illustration only and are not intended to limit the scope of the present disclosure. [Brief explanation of the drawings]

[0028] The accompanying drawings, which form a part of this specification, illustrate aspects of the present teachings and, together with the following description, explain the principles of the present disclosure. However, these drawings are drawn with some details simplified to facilitate understanding of the present teachings, and priority has not been given to maintaining structural accuracy, detail, and scale.

[0029] [Figure 1] FIG. 1 illustrates a conductive polymer coating composition according to an embodiment of the present disclosure. [Figure 2] FIG. 1 illustrates a conductive object according to an embodiment of the present disclosure. [Figure 3] FIG. 1 illustrates a method for making a conductive polymer coating composition according to an embodiment of the present disclosure. [Figure 4] FIG. 1 illustrates a method of applying a conductive polymer coating composition according to an embodiment of the present disclosure. [Figure 5] FIG. 1 is a flow diagram illustrating a method for manufacturing and using an aircraft. [Figure 6] FIG. 1 is a block diagram illustrating an aircraft. DETAILED DESCRIPTION OF THE INVENTION

[0030] Exemplary embodiments of the present teachings are described in detail below with reference to the examples illustrated in the accompanying drawings, in which generally the same reference numerals are used throughout the drawings to refer to the same or similar parts.

[0031] Throughout this specification and claims, the following terms are used with the meanings set forth herein unless clearly contradicted by the context. As used herein, phrases such as "in one embodiment," "in a particular embodiment," and "in some embodiments" may, but do not necessarily, refer to the same embodiment. Furthermore, phrases such as "in another embodiment" and "in some other embodiments" may, but do not necessarily, refer to different embodiments. As will be described below, the various embodiments can be readily combined without departing from the scope or spirit of the present disclosure.

[0032] As used herein, the term "or" is used as an inclusive operator and is synonymous with the term "and / or," unless the context clearly contradicts it. Additionally, the term "based on" is not exclusive and allows for additional, unrecited factors, unless the context clearly contradicts it. References to "at least one of A, B, and C" herein include embodiments including A, B, or C, multiple examples of A, B, or C, or combinations of A and B, A and C, B and C, A and B and B, B and B and C, A and B and C, etc. Additionally, throughout this specification, the singular also includes plural references. Furthermore, "in" includes "on" as well as "in." Similarly, embodiments of the present disclosure are construed as including, consisting of, or consisting essentially of elements A, B, C, etc., as appropriate.

[0033] Furthermore, although terms such as "first," "second," etc. are used in describing various elements herein, these terms do not limit the corresponding elements. These terms are used merely to distinguish one element from another. For example, defining a first object, component, or step as a second object, component, or step, and alternately defining the second object, component, or step as the first object, component, or step, would not depart from the scope of the present disclosure. Although a first object, component, or step and a second object, component, or step are both objects, components, or steps, they are not identical to one another. Furthermore, when terms such as "comprise," "include," "comprises," and / or "comprises" are used herein, these terms indicate the presence of stated features, steps, processes, elements, and / or components, but do not negate the presence or addition of one or more other features, steps, processes, elements, components, and / or groups thereof. Furthermore, the term "supposing" as used herein can mean "if / when," "in the event," "upon determining," or "upon detecting," depending on the context.

[0034] All physical properties defined herein are measured at 20 to 25 degrees Celsius unless otherwise specified.

[0035] Any numerical ranges described herein should be interpreted as including each and every integer and / or fractional number between the maximum and minimum values ​​in the range, as well as both endpoints. For example, a range of 0.5% to 6% explicitly includes values ​​such as 0.6%, 0.7%, and 0.9%, as well as all values ​​up to the upper endpoint such as 5.95%, 5.97%, and 5.99%, and many other intermediate values. Similar descriptions apply to other numerical attributes and / or elemental ranges, unless the context clearly contradicts them.

[0036] Additionally, all numerical values ​​are referred to as "about" or "approximately" values, taking into account experimental error and variations that one skilled in the art can expect. All numerical values ​​and ranges in this disclosure are understood to be approximate values ​​and ranges. Furthermore, the terms "about," "substantially," "substantially," or "approximately" used in connection with any quantity or measurement mean that the stated characteristic, parameter, or value does not necessarily have to be exactly achieved. For example, any quantity may include deviations or variations due to tolerances, measurement errors, measurement accuracy limits, and other factors known to those skilled in the art, but these do not preclude the effect achieved by the associated characteristic. As used herein, "about" means a value within ±5 percent of the stated target, maximum, or minimum value.

[0037] Unless otherwise specified, all percentages and amounts given anywhere in this specification are by weight. Percentages and amounts of a material are based on the active weight of that material. For example, in a solution, the amount of active ingredient is specified based on the amount of active ingredient excluding the amount of solvent, or by the weight loss due to evaporation of the solvent.

[0038] In some embodiments, the procedures, methods, techniques, and workflows disclosed herein may combine some of the steps in the procedures, methods, techniques, and workflows, and / or the order of some of the steps may be changed.

[0039] Without being bound by any particular theory, percolation theory generally describes the percolation threshold for a mixture of conductive particles in a dielectric material. Above the percolation threshold, long-range connectivity, or conductivity, can exist. Conversely, below the percolation threshold, long-range connectivity cannot exist. From a materials and processing perspective, the percolation threshold depends on several factors, including particle shape, size, density, distribution, surface functionalization, interfacial energy, suspension stability, and the nature of the forces acting during various processing steps. For polymer coating compositions containing functional particulates, segregation, settling, or separation of the particulates can affect the ability to reach the percolation threshold and / or form a continuous network to develop conductivity.

[0040] The present inventors have surprisingly developed conductive polymer coating compositions and methods for their manufacture that include a novel material structure that provides a continuous conductive network that inhibits segregation, settling, or separation of the conductive components.

[0041] 1, the conductive polymer coating composition 10 can include a conductive fibrillated structure 150 and a base polymer 250. The conductive fibrillated structure 150 can include a fibrillated polymer 100 and a conductive polymer 200 grafted to the fibrillated polymer 100. The fibrillated polymer 100 provides a structural scaffold for grafting the conductive polymer 200. In some embodiments, the fibrillated polymer 100 is non-conductive.

[0042] In some embodiments, the conductive fibrillated structure 150 includes inorganic particles. For example, the conductive polymer 200 can be grafted onto the fibrillated polymer 100 in combination with inorganic particles such as ZnO, rather than alone.

[0043] The grafting of the conductive polymer 200 and / or inorganic particles can be achieved by chemical modification and chemical bonding, or by physical bonding, such as electrospinning of the fibrillating polymer and the conductive polymer together, vacuum filtration, layer-by-layer assembly process, physical vapor deposition, etc.

[0044] The conductive polymer coating composition 10 is about 10 -5 S / cm to about 10 +1 The conductive polymer coating composition 10 may have an electrical conductivity of about 10 S / cm and a thermal conductivity of about 1.1 W / m·K to about 3 W / m·K. -5 S / cm to about 10 +2 S / cm, or about 10 -4 S / cm to about 10 +1 The conductive polymer coating composition 10 may have a thermal conductivity of from about 0.5 W / m·K to about 8 W / m·K, or from about 1 W / m·K to about 5 W / m·K.

[0045] As used herein, the terms "fibrillation" or "fibrillated" refer to the rupture of a polymer into tiny fibers, or fibrils, upon exposure to heat, shear, and / or other pressure or triggering conditions. However, not all polymers are capable of fibrillating. A polymer that is capable of fibrillating but has not yet fibrillated is called a "fibrillatable polymer."

[0046] Thus, the conductive fibrillated structure 150 comprises a fibrillizable polymer 100 configured to craze under solution conditions and / or under shear stress conditions. In other embodiments, the conductive fibrillated structure comprises a fibrillating polymer 100.

[0047] The fibrillating polymer 100 can include one or more of polytetrafluoroethylene (PTFE), sulfonated tetrafluoroethylene-based fluoropolymer copolymers such as Nafion, nylon, cellulose, high density polyethylene (HDPE), or combinations thereof.

[0048] The conductive polymer coating composition 10 can include about 0.5% to about 20% by weight of the fibrillating polymer 100, or about 1% to about 15% by weight of the fibrillating polymer 100, or about 5% to about 10% by weight of the fibrillating polymer 100.

[0049] The conductive fibrillated structure 150 comprises a conductive polymer 200. For example, the conductive polymer 200 can be grafted onto the fibrillated polymer 100.

[0050] The conductive polymer 200 can include one or more of polyaniline, polypyrrole, poly(N-methylpyrrole), poly(N-ethylpyrrole), poly(N-propylpyrrole), poly(N-butylpyrrole), poly(3,4-ethylenedioxythiophene), poly(p-phenylenevinylene), 3,4-propylenedioxypyrrole, poly(p-phenylenevinylene), 3,4-propylenedioxypyrrole, 3,4-propylenedioxythiophene, polyfuran, derivatives and copolymers thereof, or combinations thereof.

[0051] The conductive polymer coating composition can include about 1% to about 25% by weight of the conductive fibrillated structure 150, or about 1% to about 20% by weight of the conductive fibrillated structure 150, or about 5% to about 20% by weight of the conductive fibrillated structure 150.

[0052] In some embodiments, the conductive polymer coating composition 10 further comprises one or more conductive additives. The one or more conductive additives may be electrically and / or thermally conductive additives. The one or more conductive additives may include carbonaceous materials such as carbon nanotubes, graphene, and graphite; conductive pigments; metal particles; polyaniline; polypyrrole poly(3,4-ethylenedioxythiophene); nitrides such as aluminosilicates, boron nitride, aluminum nitride, zirconium nitride, tungsten nitride, vanadium nitride, tantalum nitride, and niobium nitride; carbides; polybenzoxazines; inorganic oxides such as silica and zirconia; or combinations thereof. The nitrides described above may include zirconium nitride, tungsten nitride, vanadium nitride, tantalum nitride, and niobium nitride.

[0053] The conductive polymer composition can include about 0.1% to about 15% by weight of the conductive material. For example, the conductive polymer coating composition can include about 0.1% to about 10% by weight, or about 0.2% to about 8% by weight of the conductive material. The conductive material can include one or more conductive additives in addition to the total amount of conductive polymer 200.

[0054] For example, the conductive polymer coating composition can include about 0.1% to about 15% by weight of conductive polymer 200, or about 0.1% to about 10% by weight of conductive polymer 200, or about 1% to about 10% by weight of conductive polymer 200.

[0055] The conductive polymer coating composition can include about 0.1% to about 10% by weight of the conductive additive, or about 0.5% to about 10% by weight of the conductive additive, or about 1% to about 10% by weight of the conductive additive.

[0056] The conductive polymer coating composition can include about 0.05% to about 5% by weight of the carbonaceous material, or about 0.1% to about 5% by weight of the carbonaceous material, or about 1% to about 5% by weight of the carbonaceous material.

[0057] The conductive polymer coating composition can include about 0.01% to about 5.0% by weight of metal particles, or about 0.01% to about 3% by weight of metal particles, or about 0.01% to about 1% by weight of metal particles.

[0058] The metal particles may include particles of gold (Au), silver (Ag), zinc (Zn), and / or nickel (Ni), ferromagnetic materials such as copper (Cu), iron-nickel (Fe—Ni) alloys, and iron-cobalt (Fe—Co) alloys, or combinations thereof.

[0059] In some embodiments, the conductive fibrillated structure 150 can further include one or more conductive additives. In other embodiments, the conductive polymer 200 can include one or more conductive additives. The conductive polymer 200 can be, for example, a composite conductive polymer that includes one or more conductive additives, such as a polymer composite that includes a ferromagnetic material with high magnetic permeability and a small volume fraction of an intrinsically conductive material, such as carbon nanotubes.

[0060] The conductive fibrillated structure 150 can include up to about 10% by weight of the conductive additive. For example, the conductive fibrillated structure 150 can include about 0.01% to about 10% by weight of the conductive additive, or about 0.5% to about 8% by weight of the conductive additive, or about 0.5% to about 3% by weight of the conductive additive.

[0061] The conductive polymer coating composition 10 includes a base polymer 250. The base polymer 250 can include one or more of an epoxy, an acrylic, a polyurethane, a polysiloxane, a polycarbonate, a polysilazane, a styrene-butadiene rubber, a styrene block copolymer (a thermoplastic elastomer), an acetonitrile butadiene styrene, a polyamide, a polyether ketone, a polyethylene terephthalate, derivatives thereof, or combinations thereof. In some embodiments, the base polymer 250 can include one or more conductive additives.

[0062] The conductive polymer coating composition 10 can include about 20% to about 90% by weight of the base polymer 250, about 20% to about 80% by weight of the base polymer 250, about 35% to about 75% by weight of the base polymer 250, or about 20% to about 65% by weight of the base polymer 250.

[0063] For example, base polymer 250 can include about 60% to about 90% by weight acrylic, about 65% to about 85% by weight acrylic, or about 70% to about 80% by weight acrylic. Base polymer 250 can include about 20% to about 60% by weight epoxy, about 20% to about 50% by weight epoxy, or about 30% to about 50% by weight epoxy. Base polymer 250 can include about 40% to about 70% by weight polyurethane, about 45% to about 65% by weight polyurethane, or about 50% to about 60% by weight polyurethane.

[0064] In some embodiments, the conductive polymer coating composition 10 can further include one or more solvents. For example, the base polymer 250 can be dissolved in a solvent. In other embodiments, the conductive fibrillated structure 150 can also include a solvent.

[0065] For example, the conductive polymer coating composition 10 can include from about 15% to about 40% by weight of solvent, from about 5% to about 20% by weight of solvent, or from about 10% to about 18% by weight of solvent.

[0066] The solvent can include one or more of hexane, acetone, N-methyl-2-pyrrolidone, xylene, water, methyl ethyl ketone, dimethylacetamide, cymene, toluene, cyclohexane, α- and β-pinene, hexafluoroisopropanol, dimethylformamide, dimethyl sulfoxide, or combinations thereof. In some embodiments, the solvent is water or consists essentially of water.

[0067] As described above, the conductive polymer coating composition 10 includes a conductive fibrillated structure 150 and a base polymer 250. In some embodiments, the conductive fibrillated structure 150 forms a reinforcement phase through the base polymer. As used herein, the term "reinforcement phase" refers to an open structured entangled mass of microfibers that reinforces / promotes functional requirements, such as conductivity.

[0068] In some embodiments, the conductive fibrillated structure 150 forms a continuous conductive network through the base polymer 250 and the conductive polymer coating composition 10. As used herein, the term "continuous conductive network" refers to a structure that can maintain conductivity above the percolation threshold throughout the various processing steps, including preparation, deposition, and curing of the conductive polymer coating composition 10. In other embodiments, the "continuous conductive network" is not subject to, or is subject to minimal, separation of the conductive elements in the polymer coating composition 10 throughout the various processing steps, including preparation, deposition, and curing of the conductive polymer coating composition 10.

[0069] In some embodiments, fibrillating polymer 100 is non-reactive. For example, fibrillating polymer 100 is non-reactive with at least one of conductive polymer 200, one or more conductive additives, and / or base polymer 250.

[0070] In some embodiments, the conductive polymer coating composition 10 can further include one or more functional additives. The one or more functional additives can include a pigment, a filler, a corrosion inhibiting pigment, a viscosity agent, a rheology agent, a grafting agent, an adhesion promoter, a surfactant, a plasticizer, an antifoaming agent, a flame retardant, a wetting agent, or a combination thereof. The functional additive can include, for example, one or more of acrylic acid, polyethylene oxide, styrene sulfonic acid, camphorsulfonic acid, N,N-dimethylacrylamide, dodecylbenzenesulfonic acid, sulfonyldiphenol, thymol, or a combination thereof.

[0071] The density of the base polymer 250 is, for example, about 0.9 g / cm 3 to about 2 g / cm 3 The density of the conductive fibrillated structure 150 is, for example, about 0.7 to about 1.5 cm 3 is.

[0072] The conductive polymer coating composition 10 may have a hardness measured as H or greater using a pencil hardness test according to ASTM D3363.

[0073] The conductive polymer coating composition 10 can have a peel adhesion strength measured from about 12 to about 20 MPa when tested according to ASTM D 4541. In other embodiments, the conductive polymer coating composition 10 can have a peel adhesion strength measured from about 12 to about 18 MPa, or from about 12 to about 16 MPa when tested according to ASTM D 4541.

[0074] The conductive polymer coating composition 10 may have a toughness impact resistance measured at 7 Joules or greater when tested according to ASTM D2794.

[0075] The conductive polymer coating composition 10 can have a corrosion resistance measured in a salt spray test according to ASTM B117 of greater than 3000 hours.

[0076] In some embodiments, the conductive polymer coating composition 10 is optically transparent. For example, the conductive polymer coating composition 10 has an optical transparency of about 65% to about 95%. In other embodiments, the conductive polymer coating composition 10 can have an optical transparency of about 65% to about 90%, or about 69% to about 75%. The transparency of the conductive polymer coating composition 10 can be determined using UV-Vis spectroscopy.

[0077] 2, the conductive polymer coating composition 10 can be applied to the exterior surfaces of the aircraft 300, including the windows 302, and the conductive polymer coating composition 10 can be optically transparent after drying and / or curing. When applied to the aircraft 300, the conductive polymer coating composition 10 can form an optically transparent, continuous conductive network in the area where the conductive polymer coating composition 10 is applied. In other embodiments, the conductive polymer coating composition 10 can be applied to various characterization equipment, such as electronic device display screens and scanning electron microscopes, and the conductive polymer coating composition 10 can be optically transparent after drying and / or curing and form a continuous conductive network in the area where the conductive polymer coating composition 10 is applied.

[0078] Thus, a conductive object can include the conductive polymer coating composition 10 described above, where the conductive polymer coating composition 10 provides a continuous conductive network in the area where it is applied. Such a conductive object includes, for example, an aircraft 300 having the conductive polymer coating composition 10 of the present disclosure. In some embodiments, in an aircraft 300 having the conductive polymer coating composition 10, the conductive polymer coating composition 10 can be applied to an aircraft window 302, where the conductive polymer coating composition 10 after drying and / or curing is optically transparent. The conductive polymer coating composition 10 can provide a continuous conductive network in the area where it is applied, including the aircraft window.

[0079] Figure 3 illustrates an example of a method that can be used to prepare the conductive polymer coating composition 10 described above, for example, as shown in Figure 1. Accordingly, the following description will refer to the various components shown in Figure 1.

[0080] As shown in FIG. 3, method 800 includes process 810 for producing a conductive fibrillated structure 150, process 820 for producing a base polymer 250, and process 830 for mixing the base polymer 250 with the conductive fibrillated structure 150.

[0081] The process 810 for producing the conductive fibrillated structure 150 can include a process 840 for fibrillating the fibrillizable polymer 100, a process 850 for producing the conductive polymer 200, and a process 860 for grafting the conductive polymer 200 onto the fibrillated polymer 100.

[0082] In some embodiments, the process 840 of fibrillating the fibrillizable polymer 100 includes one or more of solvent crazing the fibrillizable polymer 100, shearing the fibrillizable polymer 100, electrospinning the fibrillizable polymer 100, biaxially stretching the fibrillizable polymer 100, wet-, dry-, and melt-spinning the fibrillizable polymer 100, or combinations thereof. The fibrillating polymer 100 can include one or more of polytetrafluoroethylene (PTFE), sulfonated tetrafluoroethylene-based fluoropolymer copolymers such as Nafion, nylon, cellulose, high density polyethylene (HDPE), or combinations thereof.

[0083] The fibrillizable polymer 100 can be fibrillated in the presence of one or more conductive additives, and the conductive fibrillated structure 150 can include one or more conductive additives. The one or more conductive additives can include carbonaceous materials, conductive pigments, metal particles, polyaniline, polypyrrole poly(3,4-ethylenedioxythiophene), aluminosilicates, boron nitride, aluminum nitride, nitrides, carbides, polybenzoxazine, or combinations thereof. The nitrides mentioned above can include zirconium nitride, tungsten nitride, vanadium nitride, tantalum nitride, and niobium nitride.

[0084] The fibrillizable polymer 100 can be fibrillated in the presence of one or more functional additives, and the conductive fibrillated structure 150 can include one or more functional additives. The one or more functional additives can include pigments, fillers, corrosion-inhibiting pigments, thickeners, rheological agents, grafting agents, adhesion promoters, surfactants, plasticizers, defoamers, flame retardants, or combinations thereof. For example, the one or more functional additives can include fillers such as titanium dioxide (TiO), mica, silica, or aluminum stearate. The addition of pigments or fillers to the conductive fibrillated structure 150 can improve the opacity and / or glassiness, i.e., transparency, of the conductive polymer coating composition 10.

[0085] In some embodiments, the process 840 for fibrillating the fibrillizable polymer 100 involves fiberizing the fibrillizable polymer 100 to form a fibrillated mass of fibril fibers in which one or more conductive additives and / or one or more functional additives are embedded or entangled in a network.

[0086] The process 850 for producing the conductive polymer 200 can include dissolving a monomer in a solvent, such as an acid. The monomer can correspond to the building block of the conductive polymer 200 used, and the solvent can correspond to the type of monomer and dopant. The monomer can correspond to one or more of polyaniline, polypyrrole, poly(N-methylpyrrole), poly(N-ethylpyrrole), poly(N-propylpyrrole), poly(N-butylpyrrole), poly(3,4-ethylenedioxythiophene), poly(p-phenylenevinylene), 3,4-propylenedioxypyrrole, poly(p-phenylenevinylene), 3,4-propylenedioxypyrrole, 3,4-propylenedioxythiophene, polyfuran, derivatives and copolymers thereof, or combinations thereof.

[0087] For water-soluble monomers / polymers, the solvent may be water. The solvent may also include acids such as hydrochloric acid, oxalic acid, and benzoic acid. In other embodiments, depending on the conductive polymer 200 used, the solvent may be acetone, n-methyl-2-pyrrolidone (NMP), or hexane. In still other embodiments, the solvent may include one or more of hexane, acetone, N-methyl-2-pyrrolidone, xylene, water, methyl ethyl ketone, dimethylacetamide, cymene, toluene, cyclohexane, α- and β-pinene, hexafluoroisopropanol, dimethylformamide, dimethyl sulfoxide, or combinations thereof.

[0088] The conductive polymer 200 in process 850 may further include an oxidizing agent, such as ferric chloride, ammonium persulfate, etc., to initiate polymerization of the monomer units.

[0089] The conductive polymer 200 in process 850 may further include dopants such as benzoates, oxalates, chlorides, etc. as acids to disperse the monomers prior to polymerization.

[0090] The conductive polymer 200 in process 850 can further include one or more conductive additives. The one or more conductive additives can include carbonaceous materials, conductive pigments, metal particles, polyaniline, polypyrrole, poly(3,4-ethylenedioxythiophene), aluminosilicates, boron nitride, aluminum nitride, nitrides, carbides, polybenzoxazine, or combinations thereof. The nitrides mentioned above can include zirconium nitride, tungsten nitride, vanadium nitride, tantalum nitride, and niobium nitride. The conductive polymer 200 in process 850 can be, for example, a composite conductive polymer 200 containing one or more conductive additives, such as a polymer composite containing a high-permeability ferromagnetic material and a small volume fraction of an intrinsically conductive material, such as carbon nanotubes or graphene.

[0091] In other embodiments, polymerization of a conductive polymer 200 with inorganic particles can be used to form a composite conductive polymer 200. For example, polymerization of aniline in the presence of ZnO nanoparticles can form a polyaniline-ZnO composite, although monomers other than aniline can also be used in combination with other inorganic particles.

[0092] The process 860 of grafting the conductive polymer 200 onto the fibrillating polymer 100 may include one or more of in-situ polymerization of the conductive polymer 200 and the fibrillating polymer 100, fibril surface functionalization of the fibrillating polymer 100 with the conductive polymer 200, fibril surface modification of the fibrillating polymer 100 with the conductive polymer 200, or combinations thereof.

[0093] For example, in-situ polymerization of the conductive polymer 200 and the fibrillating polymer 100 can include reacting the monomers that make up the conductive polymer 200 with the fibrillating polymer 100. The acid-anionic part can be a dopant for the conductive polymer 200. In some embodiments, depending on the monomers used, an adhesion promoter can be used to promote bonding between the conductive polymer 200 and the fibrillating polymer 100.

[0094] Fibril surface functionalization of the fibrillating polymer 100 with the conductive polymer 200 can include reacting the fibrillating polymer 100 with the conductive polymer 200 in the presence of a functionalizing or grafting agent such as acrylic acid, polyethylene oxide (PEO), styrene sulfonic acid (NaSS), and N,N-dimethylacrylamide (DMAA). Fibril surface functionalization can include silane treatment as an intermediate step to enhance bonding between the conductive polymer 200 and the fibrillating polymer 100.

[0095] The fibril surface modification of the fibrillated polymer 100 with the conductive polymer 200 can include reacting the functionalized fibrillated polymer 100 with the monomers that make up the conductive polymer 200 together with an oxidizing agent such as ferric chloride or ammonium persulfate and a dopant as an acid to disperse the monomers. The acid can include hydrochloric acid, benzoic acid, and / or oxalic acid.

[0096] In some embodiments, the process 840 of fibrillating the fibrillizable polymer 100 involves fiberizing the fibrillizable polymer 100 to form an aggregate of fibril fibers in which the conductive polymer 200 is embedded or entangled in a network.

[0097] The process 820 to produce the base polymer 250 can include dissolving the base polymer 250 in a solvent. The base polymer 250 can include one or more of an epoxy, an acrylic, a polyurethane, a polysiloxane, a polycarbonate, a polysilazane, a styrene-butadiene rubber, a styrene block copolymer (a thermoplastic elastomer), an acetonitrile butadiene styrene, a polyamide, a polyether ketone, a polyethylene terephthalate, derivatives thereof, or combinations thereof.

[0098] The solvent can include one or more of hexane, acetone, N-methyl-2-pyrrolidone, xylene, water, methyl ethyl ketone, dimethylacetamide, cymene, toluene, cyclohexane, α- and β-pinene, hexafluoroisopropanol, dimethylformamide, dimethyl sulfoxide, or combinations thereof. In some embodiments, the solvent can be selected to match the selection of base polymer 250.

[0099] The base polymer 250 in operation 820 can further include one or more conductive additives, such as carbonaceous materials, conductive pigments, metal particles, polyaniline, polypyrrole poly(3,4-ethylenedioxythiophene), aluminosilicates, boron nitride, aluminum nitride, nitrides, carbides, polybenzoxazine, or combinations thereof. The nitrides mentioned above can include zirconium nitride, tungsten nitride, vanadium nitride, tantalum nitride, and niobium nitride.

[0100] The base polymer 250 in operation 820 can further include one or more functional additives. The one or more functional additives can include pigments, fillers, corrosion-inhibiting pigments, thickeners, rheological agents, grafting agents, adhesion promoters, surfactants, plasticizers, defoamers, flame retardants, activators, or combinations thereof. For example, the base polymer 250 can optionally include an activator that catalyzes a curing reaction under certain conditions. The one or more functional additives can include a block copolymer as a compatibilizer. Adding a pigment or filler to the base polymer 250 can improve the opacity and / or glassiness, i.e., transparency, of the conductive polymer coating composition 10.

[0101] The process 830 of mixing the base polymer 250 with the conductive fibrillated structure 150 can include mixing about 1 wt % to about 15 wt % of the conductive fibrillated structure 150 with about 20 wt % to about 90 wt % of the base polymer 250, based on the total weight of the conductive polymer coating composition 10, to create a stabilized suspension.

[0102] Blending the conductive fibrillated structure 150 into the base polymer 250 can further include blending one or more functional additives. The one or more functional additives can include pigments, fillers, corrosion-inhibiting pigments, thickeners, rheological agents, grafting agents, adhesion promoters, surfactants, plasticizers, defoamers, flame retardants, or combinations thereof. For example, leveling agents and surfactants can be added as needed to create a stable suspension.

[0103] Figure 4 shows an example of a method that can be used, for example, to apply the above-described conductive polymer coating composition 10 shown in Figure 1. Accordingly, the following description will refer to various components shown in Figure 1.

[0104] As shown in FIG. 4, the method 900 includes an operation 910 of adding a curing solvent to the conductive polymer coating composition 10, an operation 920 of applying the conductive polymer coating composition 10, and an operation 930 of curing the conductive polymer coating composition 10.

[0105] The process 910 of adding a curing solvent to the conductive polymer coating composition 10 can include adding a curing solvent or curing agent to initiate crosslinking of the conductive polymer coating composition 10. The curing solvent can be adapted to meet the performance requirements of the object being coated. In other embodiments, the conductive polymer coating composition 10 can be cured by heat, moisture, and / or solvent evaporation.

[0106] The process 920 of applying the conductive polymer coating composition 10 can include brushing, spraying, or dipping the object with the conductive polymer coating composition 10. The conductive polymer coating composition 10 can be applied, for example, by high-pressure air-assisted airless electrostatic spraying, high-flow low-pressure (HVLP) spraying, and / or air electrostatic spraying. In other embodiments, the conductive polymer coating composition 10 can be applied via inkjet printing, aerosol jetting, direct write, and filament processes for 3D printing conductive structures.

[0107] The process 930 of curing the conductive polymer coating composition 10 may include air, UV, or heat curing.

[0108] Embodiments of the present disclosure have a variety of potential applications, particularly in the transportation industry, including aerospace, marine, and automotive applications, and other applications where a conductive polymer coating composition is desirable. Thus, with reference to FIGS. 5 and 6 , embodiments of the present disclosure can be used in connection with an aircraft manufacturing and service method 1000, as shown in FIG. 5 , and an aircraft 2000, as shown in FIG. 6 . The exemplary method 1000 includes pre-production steps of specification and design 1102 of the aircraft 2000 and material procurement 1104. During production, steps include component and subassembly manufacturing 1106 and system integration 1108 of the aircraft 2000. The aircraft 2000 then undergoes certification and delivery 1110 and enters service 1112. While in customer service, the aircraft 2000 undergoes routine maintenance and service 1114, including modifications, reconfigurations, refurbishments, and the like.

[0109] Each process in method 1000 may be performed or implemented by a system integrator, a third party, and / or an operator (e.g., a customer). For purposes of illustration, a system integrator may include, but is not limited to, any number of aircraft manufacturers and major system subcontractors. A third party may include, but is not limited to, any number of vendors, subcontractors, and suppliers. An operator may also be an airline, a leasing company, a military entity, a service organization, etc.

[0110] 6 , aircraft 2000 produced by exemplary method 1000 includes an airframe 2115 with a plurality of systems 2118 and an interior 2120. Examples of the plurality of systems 2118 include one or more of a propulsion system 2122, an electrical system 2124, a hydraulic system 2126, and an environmental system 2128, as well as any number of other systems. While an aerospace example is provided, the principles of the present disclosure may be applied to other industries, such as marine and automotive.

[0111] The systems and methods presented herein may be employed during any one or more stages of aircraft manufacturing and service method 1000. For example, parts and subassemblies corresponding to part and subassembly manufacturing 1106 may be fabricated or manufactured similarly to parts and subassemblies manufactured while aircraft 2000 is in service. Additionally, one or more of the apparatus embodiments, method embodiments, or a combination thereof may be employed, for example, in part and subassembly manufacturing 1106 and system integration 1108, to significantly improve, for example, the speed and cost of assembly of aircraft 2000. Similarly, one or more of the apparatus embodiments, method embodiments, or a combination thereof may be employed while aircraft 2000 is in service, for example, but not limited to, in maintenance and service 1114.

[0112] 5 and 6 illustrate an aircraft and methods of aircraft manufacture and use, the present disclosure is not limited thereto. The conductive polymer coating compositions and methods of the present disclosure can be used on spacecraft, satellites, submarines, surface ships, automobiles, tanks, trucks, power plants, or any other suitable type of object. [Example]

[0113] Aspects of the present disclosure may be further understood with reference to the following examples, which are intended to be illustrative and not limiting. Table 1 illustrates a conductive polymer coating composition 10 according to an embodiment of the present disclosure. [Table 1]

[0114] Furthermore, the present disclosure also encompasses examples according to the following appendices.

[0115] 1. A conductive polymer coating composition (10) comprising: a conductive fibrillated structure (150); a base polymer (250); The conductive fibrillated structure (150) comprises a fibrillated polymer (100) and a conductive polymer (200) grafted to the fibrillated polymer (100), The conductive polymer coating composition (10) is about 10 -5 S / cm to about 10 +1 A composition having an electrical conductivity of about 1.1 W / m·K to about 3 W / m·K.

[0116] 2. about 1% to about 25% by weight of a conductive fibrillated structure (150); about 20% by weight to about 90% by weight of a base polymer (250); About 0.5% to about 20% by weight of a fibrillating polymer (100); about 0.1% to about 15% by weight of a conductive polymer (200); 10. The composition of claim 1, wherein the base polymer (250) comprises one or more of an epoxy, an acrylic, a polyurethane, a polysiloxane, a polycarbonate, a polysilazane, a styrene-butadiene rubber, a styrene block copolymer, an acetonitrile butadiene styrene, a polyamide, a polyether ketone, a polyethylene terephthalate, a derivative thereof, or a combination thereof.

[0117] 3. The composition of claim 1 or 2, wherein the fibrillating polymer (100) comprises one or more of polytetrafluoroethylene (PTFE), sulfonated tetrafluoroethylene-based fluoropolymer copolymers such as Nafion, nylon, cellulose, high density polyethylene (HDPE), or combinations thereof.

[0118] 4. The composition of any one of Appendices 1 to 3, wherein the conductive polymer (200) comprises one or more of polyaniline, polypyrrole, poly(N-methylpyrrole), poly(N-ethylpyrrole), poly(N-propylpyrrole), poly(N-butylpyrrole), poly(3,4-ethylenedioxythiophene), poly(p-phenylenevinylene), 3,4-propylenedioxypyrrole, poly(p-phenylenevinylene), 3,4-propylenedioxypyrrole, 3,4-propylenedioxythiophene, polyfuran, derivatives and copolymers thereof, or combinations thereof.

[0119] 5. The conductive polymer coating composition (10) further comprises from about 0.1% to about 10% by weight of one or more conductive additives; 5. The composition of any one of claims 1 to 4, wherein the one or more conductive additives comprise a carbonaceous material, a conductive pigment, a metal particle, polyaniline, polypyrrole, poly(3,4-ethylenedioxythiophene), an aluminosilicate, boron nitride, aluminum nitride, a nitride, a carbide, polybenzoxazine, or a combination thereof.

[0120] 6. The composition of claim 5, wherein the conductive fibrillated structure (150) further comprises about 0.1% to about 10% by weight of the one or more conductive additives.

[0121] 7. The composition of claim 5, wherein the conductive polymer (200) is a composite conductive polymer (200) containing one or more conductive additives.

[0122] 8. further comprising about 15% to about 40% by weight of a solvent; 8. The composition of any one of claims 1 to 7, wherein the solvent comprises one or more of hexane, acetone, N-methyl-2-pyrrolidone, xylene, water, methyl ethyl ketone, dimethylacetamide, cymene, toluene, cyclohexane, α- and β-pinene, hexafluoroisopropanol, dimethylformamide, dimethyl sulfoxide, or combinations thereof.

[0123] 9. The composition of claim 8, wherein the solvent consists essentially of water.

[0124] 10. A composition according to any one of claims 1 to 9, wherein the conductive fibrillated structure (150) forms a reinforcing phase via the base polymer (250).

[0125] 11. The composition of any one of claims 1 to 10, wherein the conductive polymer coating composition (10) has one or more of the following properties: a hardness measured as H or greater in a pencil hardness test according to ASTM D3363; a peel adhesion measured as about 12 to about 20 MPa in a test according to ASTM D4541; an impact toughness measured as 7 Joules or greater in a test according to ASTM D2794; and / or a corrosion resistance measured as 3000 hours or greater in a salt spray test according to ASTM B117.

[0126] 12. A conductive object comprising the conductive polymer coating composition (10) described in Appendix 1, wherein a continuous conductive network is formed in the applied portion of the conductive polymer coating composition (10).

[0127] 13. The conductive body of claim 12, wherein the conductive polymer coating composition (10) has an optical transparency of about 65% to about 95%.

[0128] 14. A method for producing a conductive polymer coating composition (10), comprising: generating a conductive fibrillated structure (150); Producing a base polymer (250); mixing said base polymer (250) with said conductive fibrillated structure (150).

[0129] 15. Producing the conductive fibrillated structure (150) comprises: fibrillating a fibrillizable polymer (100); Producing a conductive polymer (200); 15. The method of claim 14, comprising grafting the conductive polymer (200) onto the fibrillating polymer (100).

[0130] 16. The method of claim 15, wherein fibrillating the fibrillizable polymer (100) comprises one or more of solvent crazing the fibrillizable polymer (100), shearing the fibrillizable polymer (100), electrospinning the fibrillizable polymer (100), biaxially stretching the fibrillizable polymer (100), wet-, dry-, and melt-spinning the fibrillizable polymer (100), or combinations thereof.

[0131] 17. The method of claim 15 or 16, wherein grafting the conductive polymer (200) onto the fibrillating polymer (100) comprises one or more of in-situ polymerization of the conductive polymer (200) and the fibrillating polymer (100), fibril surface functionalization of the fibrillating polymer (100) with the conductive polymer (200), fibril surface modification of the fibrillating polymer (100) with the conductive polymer (200), or a combination thereof.

[0132] As mentioned above, the present disclosure has been described with reference to exemplary embodiments. While several embodiments have been shown and described, it will be apparent to those skilled in the art that modifications of these embodiments are possible without departing from the principles and spirit of the above description. All such modifications and alterations should be construed as being included in the present disclosure insofar as they come within the scope of the appended claims and their equivalents.

Claims

1. A conductive polymer coating composition (10), comprising: A conductive fibrillated structure (150); A base polymer (250), The conductive fibrillated structure (150) comprises a fibrillated polymer (100) and a conductive polymer (200) grafted to the fibrillated polymer (100); The conductive polymer coating composition (10) is -5 S / cm to 10 +1 A composition having an electrical conductivity of 1.1 S / cm and a thermal conductivity of 1.1 W / m·K to 3 W / m·K.

2. 1 wt.% to 25 wt.% of a conductive fibrillated structure (150); 20% to 90% by weight of a base polymer (250); 0.5% to 20% by weight of a fibrillating polymer (100); 0.1% to 15% by weight of a conductive polymer (200); 10. The composition of claim 1, wherein the base polymer (250) comprises one or more of an epoxy, an acrylic, a polyurethane, a polysiloxane, a polycarbonate, a polysilazane, a styrene-butadiene rubber, a styrene block copolymer, an acetonitrile butadiene styrene, a polyamide, a polyether ketone, a polyethylene terephthalate, derivatives thereof, or combinations thereof.

3. 10. The composition of claim 1, wherein the fibrillating polymer (100) comprises one or more of polytetrafluoroethylene (PTFE), sulfonated tetrafluoroethylene-based fluoropolymer copolymers such as Nafion, nylon, cellulose, high density polyethylene (HDPE), or combinations thereof.

4. 2. The composition of claim 1, wherein the conductive polymer (200) comprises one or more of polyaniline, polypyrrole, poly(N-methylpyrrole), poly(N-ethylpyrrole), poly(N-propylpyrrole), poly(N-butylpyrrole), poly(3,4-ethylenedioxythiophene), poly(p-phenylenevinylene), 3,4-propylenedioxypyrrole, poly(p-phenylenevinylene), 3,4-propylenedioxypyrrole, 3,4-propylenedioxythiophene, polyfuran, derivatives and copolymers thereof, or combinations thereof.

5. The conductive polymer coating composition (10) further comprises 0.1% to 10% by weight of one or more conductive additives; 10. The composition of claim 1, wherein the one or more conductive additives comprise a carbonaceous material, a conductive pigment, a metal particle, a polyaniline, a polypyrrole poly(3,4-ethylenedioxythiophene), an aluminosilicate, a boron nitride, an aluminum nitride, a nitride, a carbide, a polybenzoxazine, or a combination thereof.

6. 6. The composition of claim 5, wherein the conductive fibrillated structure (150) further comprises 0.1% to 10% by weight of the one or more conductive additives.

7. The composition of claim 5 , wherein the conductive polymer (200) is a composite conductive polymer (200) that includes one or more conductive additives.

8. Further comprising 15% to 40% by weight of a solvent; The solvent is hexane, acetone, N-methyl-2-pyrrolidone, xylene, water, methyl 2. The composition of claim 1, comprising one or more of the following: diethyl ethyl ketone, dimethylacetamide, cymene, toluene, cyclohexane, α- and β-pinene, hexafluoroisopropanol, dimethylformamide, dimethylsulfoxide, or combinations thereof.

9. The composition of claim 8 , wherein the solvent consists essentially of water.

10. The composition of claim 1 , wherein the conductive fibrillated structure (150) forms a reinforcing phase through the base polymer (250).

11. The conductive polymer coating composition (10) is lead-free according to ASTM D3363. The hardness is measured as H or higher in the pen hardness test, or in the test based on ASTM D4541. Peel adhesion measured at 12 to 20 MPa or ASTM D279 4, and / or has a corrosion resistance of 3,000 hours or more in a salt spray test in accordance with ASTM B117. The composition of claim 1 having one or more of the following characteristics:

12. A conductive object comprising the conductive polymer coating composition (10) according to any one of claims 1 to 11, wherein a continuous conductive network is formed in the applied portion of the conductive polymer coating composition (10).

13. 13. The conductive body of claim 12, wherein the conductive polymer coating composition (10) has an optical transparency of 65% to 95%.

14. A method for producing a conductive polymer coating composition (10), comprising the steps of: Producing a conductive fibrillated structure (150); Producing a base polymer (250); mixing said base polymer (250) with said conductive fibrillated structure (150).

15. Producing the conductive fibrillated structure (150) comprises: Fibrillating a fibrillizable polymer (100); Producing a conductive polymer (200); grafting said conductive polymer (200) onto said fibrillating polymer (100).

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