• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
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    • 专利摘要:
    '' composite article, manufacturing process, to manufacture a laminated panel, and laminated panel '' embodiments of the invention are directed to sheet materials coated with metal or metal alloy (hereinafter. '' coated sheet material with metal '') including, but not limited to, cloths and blankets having a metallic content between one (1) and fifty (50) grams per square meter (g / m ^ 2 ^). metal-coated sheet materials can be used as such or in conjunction with prepregs, adhesives or surface forming films to provide protection against lightning strike (lsp) and / or overall conductivity, among other benefits, to the composite article resulting. in one embodiment, the sheet material coated with metal is impregnated with a resin. according to the embodiments of the invention, a metal is applied to one or two sides of the cloth or blanket by a process of coating by physical vapor deposition. the resulting metal-coated cloth or blanket can be used as a carrier in surface forming films to impart surface conductivity to impart surface conductivity; can be used as a carrier in adhesives to form joints.
    公开号:BR112012013754B1
    申请号:R112012013754
    申请日:2010-12-07
    公开日:2019-12-24
    发明作者:Abusafieh Abdel；Thomas Price Richard
    申请人:Cytec Tech Corp；
    IPC主号:
    专利说明:

    “COMPOSITE ARTICLE, MANUFACTURING PROCESS FOR MANUFACTURING A LAMINATED PANEL, AND, LAMINATED PANEL” FIELD OF THE INVENTION [001] Conductive materials for composite articles.
    BACKGROUND OF THE INVENTION [002] The materials used in the manufacture of component parts in the aerospace industry must have certain characteristics to protect the parts from damage or danger caused by common environmental events. Lightning, an example of a common environmental occurrence, can severely damage and / or puncture parts through components if such parts are not properly conductive and grounded through the aircraft. If lightning strikes a component of an aircraft's wing during flight, the event has the potential to cause a dangerous surge current in addition to causing serious physical damage to the component itself. The surge current is of particular concern because it may eventually come in contact with a fuel tank that causes an explosion to occur. As a result of a real fatal air crash caused by a lightning strike, the Federal Aviation Administration (FAA) has implemented a system to categorize multiple zones for commercial aircraft based on the likelihood and severity of being hit by lightning. Thus, it is crucial that such component parts are manufactured to have characteristics that, among other characteristics, prevent or alleviate the damage caused by lightning strikes.
    [003] Electromagnetic interference (EMI) is another electrical problem for composite parts in the aerospace industry. EMI waves consist of electrical and magnetic fields that can induce electrical transients to induce excessive energy levels in electrical wiring and fuel system probes. A method to prevent and / or reduce these
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    2/28 occurrences is to add protective materials to absorb or reflect the incident radiation. Without proper protection from these events, the waves can interfere with the operation of the aircraft's electronic and avionic equipment or even lead to the ignition of fuel tanks. The absorption losses have been shown to be proportional to the thickness, conductivity and permeability of the protective material. Conventional protection methods include housings made of cast metal and sheet metal, and plastics with conductive fillers or coatings.
    [004] Electrostatic discharge (ESD) is already another problem for composite parts in the aerospace industry. ESD is the sudden, momentary electrical current that flows between two objects at different electrical potentials caused by direct contact or induced by an electrostatic field. Non-conductive materials, paints, plastics have insulating properties and are therefore subjected to the accumulation of static charges. The resulting loads must be controlled to protect the aircraft's electronic components and fuel tanks. Conventional ESD methods include adding fibers that have static elimination characteristics to a material, for example, carbon fiber, or adding wires and / or rods to the ends of aircraft components.
    [005] The static charge is given to a material through friction. An airplane becomes loaded simply by passing through the air. The flight through precipitation (clouds or rain) increases the load accumulation, since there is more contact material. The static charge is routinely discharged into the air at sea level, which is slightly conductive, and also into the air with higher humidity. However, air with humidity below 20 percent and / or at higher altitudes is a poor conductor. The latter allows static charge to form on the surfaces of the aircraft, especially those of composite aircraft, where the cargo does not move easily. THE
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    3/28 load formation in a structure creates a voltage potential that increases with the amount of load. On metallic structures, this voltage potential is the same anywhere because the metal conducts electricity evenly. In composite structures, however, the voltage will vary. This voltage potential, in turn, generates an electric field that is more intense in areas of acute curvature such as wing tips, propeller tips, trailing edges, jet engine blade edges and edges, etc. The accumulated charge needs to move - equal charges repel and different charges attract each other. Eventually, the difference in charge between air and the structure becomes so great that the need to discharge the voltage potential dominates, resulting in a mass "discharge" of the excess charge in the atmosphere. The formation of static charge can trigger lightning in the clouds or in charged atmospheric conditions.
    [006] At the same time, such component parts must be manufactured to target certain weight requirements so that the aircraft reaches the planned distance and also to overcome the gravitational pull of its own weight to take off without using an excessive amount of fuel. In addition, such component parts must be manufactured to withstand damage in common environmental events. This characteristic is generally described as "stiffness" in relation to composites. Thus, problems of tolerance and resistance to damage for common environmental occurrences while maintaining a workable weight of these component parts must be evaluated very carefully in the manufacturing process of such parts. Several methods are used to achieve this balance in the manufacturing process.
    [007] A conventional method for providing protection against lightning strikes to component parts in the aerospace industry is the use of mesh or sheets, grid, or cloth mesh of expanded aluminum, copper, titanium or bronze, incorporated in the composite part. Although such meshes are
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    4/28 generally effective as protection against lightning strike, many of these expanded meshes / grids are difficult to handle for both production and repair. In addition, they generally require insulation materials (for example, a layer of fiberglass insulation) to prevent undesirable galvanic corrosion in the presence of other materials, especially aluminum composite structures with carbon. In addition, when used in large quantities, the expanded meshes / grids are very heavy and can significantly increase the weight of the overall part thereby decreasing the efficiency of the aircraft.
    [008] Another method of providing protection against lightning strikes is the use of metal-coated carbon fiber material embedded in the composite part. In general, carbon fibers are coated with nickel, palladium, tin, copper or a combination of them using an electrode-free galvanizing process. These metal-coated fibers can then be formed into a uniform non-woven material. The nonwoven material with metal-coated fibers is incorporated into the composite effectively by replacing the metal mesh / grid that would otherwise be necessary for adequate protection against lightning strike. Reports of composite parts having such nonwoven materials with metal-coated fibers in them are reported to have a metallic content between about sixty (60) and one hundred (100) grams per square meter (g / m 2 ) of metal. Other reports cite a metal content by weight of 10% to 65% for crude carbon fibers between 6K (6000 filaments) to 80K (80,000 filaments). Metal-coated blanket materials are made from metal-coated fibers that are lightly bonded together with non-conductive resin (eg PVA). Thus, the weight of the general composite still presents problems regarding the efficiency of the aircraft. In addition, the electrode-free galvanizing process presents manufacturing problems such as
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    5/28 as residual galvanizing currents and higher manufacturing costs. SUMMARY OF THE INVENTION [009] A support material, comprising: (i) a sheet material; and (ii) a layer of a metal or metal alloy on at least one side of the sheet material in which the metal layer has a thickness between 0.11 μ and 25 μ, the sheet material coated with metal combined with one of a film, a resin or a sheet is disclosed herein. In some embodiments, the metal layer has a thickness between 0.5 μ and 2 μ. An area weight of the metal in the metal-coated sheet material can be less than 50 grams per square meter. In some embodiments, an area weight of the metal on the metal-coated sheet material is less than 15 grams per square meter. In other embodiments, an area weight of the metal on the metal-coated sheet material is less than 5 grams per square meter. The metal-coated sheet material can be conductive, the metal-coated sheet material having a lower surface resistivity than a surface resistivity of a sheet material. The sheet material can be one of a woven cloth or a non-woven blanket. A material comprising the sheet material can be a fibrous material including carbon, glass fiber, ceramic or organic fibers including aramid, para-aramid, nylon, thermoplastic or a combination thereof.
    [0010] In some embodiments, the metal or metallic fig is one of aluminum, copper, silver, nickel, palladium, tin, gold or a combination thereof. In addition, the sheet material coated with metal can be coated by a process selected from the group consisting of physical vapor deposition, atomic layer deposition, chemical vapor deposition, low pressure chemical vapor deposition and intensified chemical vapor deposition. in plasma. The metal can be coated over the material in
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    6/28 sheet in a continuous layer. The film or plate may be one of a fibrous reinforcement in the form of a sheet, tape, crude fiber, cloth or mat and pre-impregnated with resin, an adhesive film or a surface forming film. A support material comprising the film or resin can be a polymeric material in which the polymeric material is at least one of epoxy, bismaleimide, phenolic, cyanate ester and polyimide. The sheet material can be combined with at least one sheet to form a laminated structure. Alternatively, the sheet material can be sandwiched between a plurality of sheets to form a laminated structure.
    [0011] A composite article, comprising: (i) a plurality of plates, each plate adjacent to at least one other plate; and (ii) at least one non-woven mat having a metal lining or metal beam on at least one side of it adjacent to at least one plate in which a weight of area of the lining on the non-woven mat is less than 50 grams per square meter is disclosed here. In some embodiments, the area weight of the coating is between 3 g / m 2 and 20 g / m 2 . In one embodiment, at least one non-woven mat having a metal or metal alloy coating on at least one side of it is interspersed between the plurality of sheets to form a laminated panel, the laminated panel having overall conductivity. The laminated panel can be distinguished by an increase in compression after the impact value when subjected to a force relative to a laminated panel without at least one non-woven mat having a metal or metal alloy coating on at least one side interspersed therein. . In addition, the laminated panel can be distinguished by an increase in a stiffness value when the panel is loaded after a slit is introduced therein in relation to a laminated panel without at least one non-woven mat having a
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    7/28 metal coating or metal alloy on at least one side interspersed in it. In another embodiment, at least one non-woven mat is adjacent to an outermost sheet to form a laminated panel, the laminated panel capable of mitigating damage when a voltage of up to 200,000 amps makes contact with the laminated panel.
    [0012] The metal layer on the coated non-woven mat can have a thickness between 0.5 μ and 2 μ. A material comprising the sheet material may be a fibrous material including carbon, glass fiber, ceramic or organic fibers including aramid, para-aramid, nylon, thermoplastic or a combination. In some embodiments, the metal or metallic fig may be one of aluminum, copper, silver, nickel, palladium, tin, gold or a combination thereof. In addition, the metal coated non-woven mat can be coated by a process selected from the group consisting of physical vapor deposition, atomic layer deposition, chemical vapor deposition, low pressure chemical vapor deposition and enhanced chemical vapor deposition. by plasma. The metal can be coated over the sheet material in a continuous layer. Each plate can be a fibrous reinforcement in the form of a sheet, tape, crude fiber, cloth or mat and pre-impregnated with resin. In addition, each plate can be unidirectional or almost istotropic.
    [0013] A manufacturing process, comprising: (i) positioning a sheet material having a metal or metal alloy coating on at least one side thereof where an area weight of the coated sheet material is less than 50 grams per square meter in a tool;
    (ii) position a sheet adjacent to the coated sheet material; and (iii) applying pressure and heat to the coated sheet material and at least one sheet to form a laminated panel is disclosed herein. In more detail, the area weight of the coating can be between 3 g / m 2 and 20
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    8/28 g / m 2 . The manufacturing process may further comprise positioning a plurality of adjacent sheets on the sheet adjacent to the coated sheet material. The manufacturing process can further comprise interleaving a plurality of coated sheet materials with the plurality of sheets. In some embodiments, the sheet material is a non-woven mat, more particularly, a fibrous material that includes carbon, glass fiber, ceramic or organic fibers including aramid, paraaramide, nylon, thermoplastic or a combination. In some embodiments, the metal or metallic fig is one of aluminum, copper, silver, nickel, palladium, tin, gold or a combination thereof. In some embodiments, the metal layer on the non-woven mat has a thickness between 0.5 μ and 2 μ. The metal-coated non-woven mat can be coated by a process selected from the group consisting of physical vapor deposition, atomic layer deposition, chemical vapor deposition, low pressure chemical vapor deposition and plasma-enhanced chemical vapor deposition. Each plate can be a fibrous reinforcement in the form of a sheet, tape, crude fiber, cloth or mat and pre-impregnated with resin. Each plate can be unidirectional or almost istotropic.
    BRIEF DESCRIPTION OF THE DRAWINGS [0014] FIG. IA shows SEM photographs of representative non-woven metal-coated fiberglass mats (blankets).
    [0015] FIG. 1B shows SEM photographs of the fracture surface interface with a metal-coated inter-sheet (metal-coated mat) according to the embodiments of the invention and without an inter-sheet.
    [0016] FIG. 1C shows SEM photographs of fibers coated with metal from a non-woven mat (blanket) according to the embodiments of the invention after being subjected to resistance tests and
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    9/28 stress.
    [0017] FIG. 2 illustrates values of overall resistivity values in length, width and thickness for laminates manufactured according to the embodiments of the invention compared to conventional laminates for unidirectional and quasi-isotropic specimens.
    [0018] FIG. 3 illustrates lamination of a plurality of sheets and a plurality of metal-coated non-woven blankets according to an embodiment of the invention in the process of being assembled for a vacuum bag process.
    [0019] FIG. 4 illustrates a lamination of a plurality of sheets and a non-woven metal-coated mat according to an embodiment of the invention in the process of being assembled by a vacuum bag process.
    DETAILED DESCRIPTION [0020] The following detailed description is one of the best currently considered ways of carrying out the invention. The description should not be interpreted in a limited sense, but it is made purely for the purpose of illustrating the general principles of the invention.
    [0021] Embodiments of the invention are directed to sheet materials coated with metal or alloy (hereinafter "sheet material coated with metal") including, but not limited to, cloths and blankets that have a metallic content between one (1) and fifty (50) grams per square meter (g / m 2 / m 2 ). Metal-coated sheet materials can be used as such or in conjunction with prepregs, adhesives or surface forming films to provide lightning protection (LSP) and / or overall conductivity, among other benefits, to the composite article resulting. In one embodiment, the sheet material coated with metal is impregnated with a resin. According to the forms
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    In the embodiment of the invention, a metal is applied to one or two sides of the cloth or blanket by a process of coating by physical vapor deposition. The resulting metal-coated cloth or blanket can be used as a carrier in the surface forming films to impart surface conductivity; can be used as an adhesive carrier to form conductive adhesive bonded joints; they can be intercalated (one or more blankets coated with metal) between layers of prepreg to provide surface and / or overall conductivity as well as rigidity; or they can be used to manufacture composite articles.
    [0022] In the context of this application, an "adhesive" is a bonding agent for bonding composites to composites, composites for metal and other materials (including honeycomb core materials), and metal for metal. In aerospace applications, structural adhesives reduce or eliminate mechanical fasteners and the work, weight, and holes that reduce the strength they provide. Film stickers can be supplied in roll form, and can include backing materials or "carriers". The loaders provide integrity for handling, flow of control during curing, increased adhesive strength, thickness control at the joint line and can provide conductivity for the adhesive. Chargers include low density mesh or non-woven materials such as fiberglass, quartz, carbon fiber, nylon, polyester or metal. According to embodiments of the invention, a magazine can include a sheet material coated with metal.
    [0023] In the context of this application, a "surface film" is a resin-rich layer applied to composites to fill imperfections on the surface, such as perforations, surface cracks, core marks and other imperfections, thereby reducing dependent manufacturing costs of labor required to remove these imperfections. THE
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    11/28 resin may include a carrier such as low density mesh or non-woven materials including fiberglass, quartz, carbon fiber, nylon, polyester or metal. According to embodiments of the invention, a magazine can include a sheet material coated with metal.
    [0024] In the context of this application, a "pre-impregnated" is a thin sheet of fiber impregnated with resin and directionally aligned, for example, cloth, tape or adhesive tape. In one method, prepregs are manufactured by intercrossing crude fibers (bundles of small diameter fibers) between sheets of carrier paper that are coated with a resin matrix. In the pressure of the carrier paper on the raw fibers using heated rollers, the resin melts and impregnates the fibers thus forming a prepreg. The resin matrix can include, but is not limited to, materials such as standard or hardened epoxides, bismaleimides (BMI), cyanate esters, phenolics, reaction and condensation polyimides, and combinations thereof. Fibers, or "reinforcements", may include, but are not limited to, materials such as Kevlar, fiberglass, quartz, carbon, graphite and special fibers. According to embodiments of the invention, a reinforcement can include a sheet material coated with metal.
    [0025] According to embodiments of the invention, a sheet material (i.e., a designed textile product) can be coated with a metal or combination of metals to impart a level of conductivity to the sheet material. The sheet material can be, but is not limited to, a woven or nonwoven blanket or cloth comprised of fibers or a mixture of fibers. Materials comprising the sheet material include, but are not limited to, fiberglass, carbon, thermoplastic (for example, KM 180), aramid, para-aramid (Kevlar®) and mixtures and / or combinations thereof. In some embodiments, the coating thickness can be between about 0.1 microns (μ) and about 25 μ, more accurately,
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    12/28 between about 0.5 μ and 2 μ.
    [0026] According to embodiments of the invention, the metal coating can be applied to the sheet material by a physical or chemical process that coats the sheet material with a very thin layer of metal. Such processes include, but are not limited to, physical vapor deposition (PVD), atomic layer deposition (ALD), chemical vapor deposition (CVD), low pressure CVD, plasma enhanced CVD, or any other suitable process. In one application, a PVD process is used to coat one side or both sides of the sheet material. Physical vapor deposition (PVD) is a method of depositing thin films by condensing a vaporized form of the metal onto various surfaces. The coating method involves purely physical processes and variants of the method include evaporative deposition, electron beam physical vapor deposition, ejection deposition, cathodic arc deposition and pulsed laser deposition and are known to a person skilled in the art. In any embodiment, the metal used to coat one or both sides of the sheet material includes, but is not limited to, aluminum (Al), copper (Cu), silver (Ag), palladium (Pd), tin ( Sn), gold (Au), copper-nickel (Cu-Ni), copper-aluminum (Cu-Al) combinations thereof and any other suitable metal with similar characteristics.
    [0027] Embodiments of the present invention provide a support material, which comprises a sheet material and a layer of a metal or metal beam on at least one side of the sheet material in which the metal layer has a thickness between 0.4 μ and 25 μ, the sheet material coated with metal combined with one of a film, a resin or a plate. The metal layer can have a thickness between 0.5 μ and 2 μ and the area weight of the metal on the metal-coated sheet material is less than 50 grams per square meter or more preferably less than
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    13/28 than 15 grams per square meter.
    [0028] Other embodiments of the present invention provide a composite article, comprising the plurality of sheets, each sheet adjacent to at least one other sheet and at least one non-woven mat having a metal or metal alloy coating on at least one side of the same contiguous to at least one plate in which an area weight of the coating on the non-woven mat is less than 50 grams per square meter. The area weight of the coating is between 3 g / m 2 and 20 g / m 2 . The support material for the composite article has the metal layer on the non-woven mat coated in a thickness between 0.5 μ and 2 μ and a material comprising the sheet material is a fibrous material including carbon, fiber glass, ceramic or organic fibers including aramid, paraaramide, nylon, thermoplastic or a combination. The support material for the composite article has the metal or metal frame which is one of aluminum, copper, silver, nickel, palladium, tin, gold or a combination thereof. The metal-coated non-woven mat is coated by a process selected from the group consisting of physical vapor deposition, atomic layer deposition, chemical vapor deposition, low pressure chemical vapor deposition and plasma-enhanced chemical vapor deposition and the metal is coated on the sheet material in a continuous layer in which the sheet is a fibrous reinforcement in the form of a sheet, tape, crude fiber, cloth or mat and pre-impregnated with resin.
    [0029] Another embodiment of the present invention involves a manufacturing process, which comprises positioning a sheet material having a metal or metal alloy coating on at least one side of the same where an area weight of the coated sheet material is less than 50 grams per square meter on a tool, position a plate adjacent to the coated sheet material and apply pressure and heat to the
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    14/28 coated sheet material and at least one plate to form a laminated panel. The area weight of the coating is between 3 g / m 2 and 20 g / m 2 .
    [0030] The manufacturing process may also involve placing a plurality of adjacent sheets on the sheet adjacent to the coated sheet material. The process may also involve sandwiching a plurality of coated sheet materials with the plurality of sheets.
    [0031] The manufacturing process may use a sheet material that is a non-woven mat that is manufactured from a fibrous material including carbon, fiberglass, ceramic or organic fibers including aramid, paraaramide, nylon, thermoplastic or a combination . The metal or metallic fig is one of aluminum, copper, silver, nickel, palladium, tin, gold or a combination of them in which the metal layer on the non-woven mat has a thickness between 0.5 μ and 2 μ 38.
    [0032] The manufacturing process may involve non-woven mat coated with metal that is coated by a process selected from the group consisting of physical vapor deposition, atomic layer deposition, chemical vapor deposition, low pressure chemical vapor deposition and chemical vapor deposition intensified by plasma and the plate is a fibrous reinforcement in the form of a sheet, tape, crude fiber, cloth or mat and pre-impregnated with resin.
    Conductivity Assessment.
    [0033] Electrical conductivity (σ) is an intrinsic physical property of a material regardless of the size or shape of the sample. Resistivity (p) is a physical property of a material to resist or oppose the movement of charge (current flow) through the material and is inversely related to conductivity. A material with low resistivity is highly conductive, and vice versa. According to the embodiments of the invention, the cloths and blankets can be conferred with a
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    15/28 conductive characteristic by the application of a metallic coating between about 0.4 μ and 25 μ, more particularly about 0.5 μ and 2 μ, by a physical vapor deposition process or similar process.
    EXAMPLE 1 [0034] Several blankets and cloths were coated using physical vapor deposition (PVD) to test the conductivity of the resulting metal-coated blankets and cloths. The metal was coated in one or more continuous layers. Carbon, fiberglass and thermoplastic blankets (woven and non-woven) with metallic coatings ranging from about 0.5 μ to about 2 μ in thickness (coatings on one side or on two sides) were coated using a PVD chamber .
    [0035] Fiberglass and carbon cloths (woven and non-woven) with metallic coatings ranging from about 0.5 μ to about 2 μ in thickness (one coat on one side or on two sides) were also coated using the same vacuum chamber.
    [0036] The following Table 1 lists the representative results of sheet materials coated with metal according to the embodiments of the invention and compared to standards:
    Metal Thickness (μ) Coated sides Area weight (g / m 2 / m 2 ) Area weight difference (g / m 2 / m 2 ) Carbon blanket (reference) AT AT Ν / Α 11.4 AT Carbon blanket Al i μ 1 13.5 2.1 Carbon blanket Al i μ 2 14.4 3.0 Carbon blanket Ass 1 μ 1 13.4 2.0 Carbon blanket Ass 1 μ 1 26.3 14.9 Carbon blanket Ass 1 μ 2 28.2 16.8 Fiberglass blanket (reference) AT Ν / Α Ν / Α 11.0 AT Fiberglass blanket Al ι μ 1 11.2 0.2 Fiberglass blanket Al ι μ 2 12.7 1.7 Fiberglass blanket Al ι μ 2 12.1 1.1 Fiberglass blanket Al 0.5 1 -11.1 -0.1 Fiberglass blanket Al 2μ 1 11.5 0.5 Fiberglass blanket Ass ι μ 1 15.4 4.4 Carbon Cloth AT Ν / Α Ν / Α 205 AT
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    16/28
    Carbon Cloth Ass i μ 1 210 10 Carbon Cloth Ass 1 μ 2 217 12
    TABLE 1 [0037] As illustrated by Table 1 above, sheet materials coated with metal using a PVD process resulted in metal coated blankets with a metal area weight of less than 5 g / m 2 . Similarly, sheet materials coated with metal using a PVD process resulted in cloths coated with metal with a metal area weight of less than 15 g / m 2 . Thus, sheet materials coated with metal according to the embodiments of the invention resulted in a very low weight blanket, for example, an increase of about five (5) g / m 2 for blankets and an increase of about fifteen (15) g / m 2 for cloths when compared, for example, with prior art blankets incorporating metal that have a final area weight of at least one hundred (100) g / m 2 or greater (for example, the combined weight of the blanket and metal). [0038] Furthermore, sheets coated with metal according to the embodiments of the invention have been experimentally shown to have a significant decrease in surface resistivity (and therefore a significant increase in conductivity) when compared to the prior art sheets . For example, a conventional carbon blanket (8 g / m 2 ) with no metallic coating has been found to have an average surface resistance of 5 ohms. By comparison, a carbon mat coated with silver metal (between about 2 μ to 5 μ in metal thickness) according to the embodiments of the invention was found to have an average surface resistance of 11.2 milli-ohms. Similarly, a carbon blanket coated with copper metal (between about 2 μ to 5 μ thickness of metal according to the embodiments of the invention was found to have an average surface resistance of 75.2 milli-ohms. The comparison data for samples prepared according to the
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    17/28 invention therefore show a decrease in surface strength of at least fifty (5) times compared to that of a conventional sample. A Digital Megger DLROIOX Low Resistance ohmometer was used to measure the resistance of the samples.
    [0039] Metal-coated blankets and cloths according to the embodiments of the invention can be used in a variety of applications to manufacture composite articles, for example, in the aerospace industry. In one embodiment, the metal-coated webs can be sandwiched with pre-impregnated sheets to form a laminate with conductive properties or applied as a surface layer to a plurality of stacked sheets. The resulting laminates have been experimentally shown to withstand a radius drop in Zone IA (200,000 amps) and, in the interleaved embodiment, experimentally shown to exhibit overall conductivity as well as increased stiffness.
    [0040] Representative laminates that incorporate a blanket or blankets coated with metal (on one side or on two sides) according to the embodiments of the invention and sandwiched between sheets were prepared according to the following example.
    EXAMPLE 2 [0041] The laminates were manufactured to determine the effect of overall strength through the laminate of the interlayered blanket, coated with metal. The mechanical properties of these laminates have also been tested. The pre-impregnated sheets (i.e., carbon cloth pre-impregnated with 0% or 10% hardened particle) were assembled by known methods with and without metal-coated blankets interspersed according to the embodiments of the invention. Both unidirectional and almost isotropic laminates were tested.
    [0042] The following Table 2 lists representative results of resistivity measurements of laminates prepared with at least one mat
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    18/28 coated with metal according to the embodiments of the invention and compared to standards:
    Guidance Thickness Global resistivity (ohm-cm) Cm Through the thickness Through width Through the length 0% rigid, no blanket (0) 26 0.373 1358 50.0 0.042 0% rigid, Cu coated blanket (0) 26 0.386 17.2 0.147 0.012 10% rigid, no blanket (0) 26 0.391 > 10,000 13.6 0.026 10% rigid, Cu coated blanket (0) 26 0.396 33.2 0.111 0.010 10% rigid, blanket coated with aluminum (0) 26 0.401 1351 0.521 0.011 OHC - 0% rigid, no blanket (45.0, -45.90) 2s 0.226 > 10,000 0.208 0.051 OHC - 0% rigid, Cu coated blanket (45.0, -45.90) 2s 0.234 51.3 0.075 0.012 Elastic - 10% hard, no blanket (0) 8 0.117 8768 11.0 0.017 Elastic - 10% hard, blanket coated with Al (0) 8 0.124 1821 0.402 0.007
    TABLE 2 [0043] Prepregs such as carbon cloth infused with epoxy resins are generally non-conductive in view of the resin incorporated in them and, therefore, the electric current is greatly inhibited from passing through them. Similarly, blankets made from organic, fiberglass or synthetic material (used in interleaving in the manufacture of laminated panels) are generally non-conductive. Therefore, a conventional laminate formed with one or more conventional pre-impregnated plates and one or more conventional blankets in general will not exhibit any overall conductivity or surface or low conductivity (unless a mesh or sheet metal is incorporated into them).
    [0044] Because the metal-coated blankets according to the embodiments of the invention were sandwiched between non-conductive sheets, it would be anticipated that the resulting laminates may show some conductivity but would exhibit little to no overall conductivity. This would be
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    19/28 expected since it would be reasonable to assume that there was not an adequate number of conductive paths between the plates based on interleaving. [0045] However, as shown in Table 2, improvements in conductivity through thickness (measured as resistivity in Ohmscm) in laminates manufactured according to the embodiments of the invention are between one to three orders of magnitude compared with conventional laminates (no interleaving blanket). Improvements were also seen in conductivity across width and across length (see Table 2). These results were unexpected since, in order to provide conductivity through the thickness, there must be an adequate number of conductive paths between the plates.
    [0046] Although laminates manufactured in accordance with the embodiments of the invention exhibited unexpectedly high overall conductivity characteristics, the overall cured sheet thickness (CPT) does not increase significantly compared to non-interleaved laminates. It has been experimentally shown that the CPT of laminates manufactured according to the embodiments of the invention increased by less than 3.5% compared to non-interleaved laminates.
    Morphology [0047] An investigation was conducted to elucidate the morphology of sheet materials coated with metal according to the embodiments of the invention. A Scanning Electron Microscope (SEM) was used to photograph the blankets coated with metal in polished cross-section.
    [0048] FIG. IA show SEM photographs of representative metal-coated fiberglass blankets. Because PVD is a surface coating process, it was predicted that the metal or metal alloy coating would be limited to a layer of a certain thickness on the
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    20/28 surface of the blanket. However, SEM photographs revealed that the metal was able to penetrate the interstitial spaces (to some degree) between the randomly ordered "weft" of the blanket fibers resulting in coated fibers and coated groups of coated fibers. For fibers (or groups of fibers) that are in contact with each other at various points, for example, adjacent fibers or crossed fibers, the forms of metal coating around the adjacent fibers or the crossing point as if they were “a ”Fiber. Thus, as a result of the randomly ordered nature of the fibers in the mat, metallic "wefts" are formed throughout the mat when subjected to the PVD surface coating process. When interspersed between pre-impregnated sheets to form a laminated panel, these metallic “wefts” form connective bridges between the sheets. As a result, laminated panels manufactured in accordance with the embodiments of the invention exhibited unexpectedly high overall conductivity characteristics.
    [0049] Compared with the processes of conferring conductivity of the prior art in which the fibers are coated (for example, by electroplating without electrode) and then formed on a non-woven mat or cloth, the non-woven mats and cloths are coated on a surface (one side) or surface (two sides) by PVD or an equivalent process. This provides sufficient protection against lightning strike to the resulting laminate panel while not significantly increasing the weight of the mat or cloth.
    [0050] For example, non-woven mats manufactured according to the prior art methods (eg electroplating without electrode) have a final area weight of approximately one hundred (100) g / m 2 when compared to non-woven mats manufactured from according to the embodiments of the invention which have metal weights below five (5) g / m 2 and about fifteen (15) g / m 2 for cloths.
    Petition 870190100933, of 10/8/2019, p. 28/77
    21/28
    Mechanical properties [0051] In addition to the unexpected results with respect to conductivity (as described above), laminates manufactured according to the embodiments of the invention unexpectedly exhibited an increase in stiffness and resistance / damage tolerance without adversely affecting tensile strengths or compressive when compared to laminates manufactured without any interleaving. The following table highlights the enhanced mechanical properties:
    D% of rigid plates with 10% of rigid plates with interleaved layers coated interspersed layers coated with metal with metal Impact After Compression (CAI / ksi) 40 to 50% increase in CAI in non-interleaved laminates No appreciable change Rigidity (Gic / J / m 2 ) > 100% increase in Gi c in non-interleaved laminates ~ 40% increase in Gi c over non-interleaved laminates Tensile strength No appreciable change No appreciable change Traction strain No appreciable change No appreciable change Compressive strength No appreciable change No appreciable change
    TABLE 3 [0052] Compression After Impact, or CAI, is a measure of the resistance / tolerance to damage of a laminate. Damage resistance measures the integrity of the laminate when it experiences a falling weight impact event while damage tolerance measures the integrity of the laminate after being subjected to an almost static static indentation. In general, the higher the CAI value, the more the laminate is resistant / tolerant to damage. Stiffness, or Gi c , is a measure of the laminate's resistance to the propagation of a crack. Stiffness is measured by the load of a sample containing a deliberately induced crack of a given length, calculating a fracture stiffness (Ki c ), then calculating a stiffness using the fracture stiffness value and other constants. In general, the higher the Gi c value, the more the laminate is resistant to micro-cracking. FIG. 2 illustrates overall resistivity values in length, width and thickness for laminates manufactured from
    Petition 870190100933, of 10/8/2019, p. 29/77
    22/28 according to the embodiments of the invention and conventional laminates for both unidirectional (0) 26 and quasi-isotropic (45.0, -45.90) 2s specimens. As shown, laminates manufactured according to the embodiments of the invention show improved conductivity in overall resistivity in length, width and thickness compared to conventional laminates in each specimen.
    [0053] As shown in Table 3, the mechanical properties of resistance / damage tolerance (CAI) and stiffness (Gic) for laminated panels were greatly enhanced with the metal-coated blanket interspersed according to the embodiments of the invention when compared laminated panels without any interleaved specimen. In addition, the simultaneously modified laminated panels exhibited little to no effect on the tensile or compressive strength properties.
    [0054] Thus, laminated panels manufactured with blankets coated with metal according to the embodiments of the invention and interspersed in it resulted in multifunctional laminated panels. More particularly, laminated panels according to the embodiments of the invention resulted in multifunctional laminated panels with enhanced functionality with respect to overall conductivity, mechanical properties (for example, strength and stiffness) and passing Zone drop tests. IA.
    [0055] In addition to the above, scanning electron microscopy (SEM) images were taken to study the multifunctional laminates manufactured in accordance with the embodiments of the invention after several tests of tension, effort and impact were performed on the structures. It was found that the metal-coated interlayer (in this case, fiberglass) provided a fibrous interface creating a tortuous path to suppress the delamination and crack propagation (see FIG. 1B). Beyond
    Petition 870190100933, of 10/8/2019, p. 30/77
    23/28 In addition, it was found that the deformation energy was uniform as the specimens were loaded. In addition, it was discovered that the cracks conferred to the laminate remained within the same action. In addition, it was discovered that the metal coating remained intact after being subjected to various damage-inducing events (see FIG. 1C).
    Resistance to environmental impact [0056] As a result of a real fatal air accident caused by a lightning strike, the Federal Aviation Administration (FAA) has implemented a system to categorize various zones for the commercial aircraft based on the likelihood and severity of being hit by lightning. Areas of interest are categorized as Zones IA at 1C, 2A at 2B and 3, with Zone IA (200,000 amps) being the most crucial in terms of withstanding a lightning strike.
    [0057] Laminated panels manufactured according to the embodiments of the invention were subjected to simulated radius drops of up to 200,000 amps. To test the degree of protection against lightning strike (LSP), the test panels were painted on the side of the lightning strike with an epoxy based coating and urethane top coating in typical aerospace thickness. A panel of 8 hardened carbon / epoxy sheets having a blanket coated with metal (silver or copper) according to the embodiments of the invention and subjected to a Zone IA test produced the following results: (i) the damage was limited approximately
    1.5 to 2.5 plates; the rear side of the test panel was unaffected; and (iii) the delamination area was determined to be about seven (7) in 2 (45.2 cm 2 ) to eight (8) in 2 (51.6 cm 2 ). For comparison purposes, a panel of 8 carbon / epoxy sheets hardened without a metal-coated blanket and subjected to a Zone IA test produced the following results: (i) damage through all eight plates with a hole in the rear side of the panel and (ii) area
    Petition 870190100933, of 10/8/2019, p. 31/77
    24/28 delamination around thirty-six (36) in 2 (232.2 cm 2 ). Thus, laminated panels according to the embodiments of the invention have been shown to be very effective as protection against lightning strike (LSP) compared with panels of the prior art.
    [0058] In addition to showing sufficient LSP, it is anticipated that laminate panels will protect from other potentially damaging electrical events such as electrostatic discharge (ESD), static charge formation, electromagnetic interference (EMI), glowing potential at the edge of the wing , current return network (CRN) and high intensity related fields (HIRF).
    [0059] FIG. 3 illustrates lamination of a plurality of sheets and a plurality of nonwoven blankets coated with metal according to an embodiment of the invention in the process of being assembled by a vacuum bag process. As shown, a lamination 300 comprised of a plurality of metal-coated blankets 302 interspersed with a plurality of cloth sheets 304 (i.e., contiguous) is prepared by layering a blanket 302, then a cloth sheet 304, and then repeating until the desired number of layers is obtained. The 304 cloth sheets can be unidirectional, woven or multiaxial (i.e., unfolded cloths) and can be positioned in a unidirectional, almost isotropic or orthotropic orientation as known to a person of ordinary skill in the art. The metal-coated blanket 302 can be any of the embodiments as previously described. The cloth sheet can be made of fiberglass, carbon, aramid fibers or any other suitable fiber.
    [0060] Lamination 300 can be positioned in a mold or tool 306 in which the surface of tool 306 is pre-prepared by positioning adhesive tape 308 around a periphery thereof, a
    Petition 870190100933, of 10/8/2019, p. 32/77
    25/28 gasket felt 310 (eg Armalon® felt) and a 312 boat cloth over it. Fiberglass filaments 314 can be positioned to define an edge of a silicone barrier 316. A resin film 318 such as fluorinated ethylene-propylene copolymer (FEP) can be positioned on lamination 300 followed by a pressure plate 320, a or more layers of fiberglass 322 and sealed by a vacuum bag 324. The system is in communication with one or more holes, such as vacuum hole 326. Pressure and heat are applied to it to cure the multifunctional pre-impregnated plates forming this the laminated panel with overall conductivity and intensified stiffness and resistance. It should be appreciated that other processes can be used to form prepregs according to embodiments of the invention such as, but not limited to, an autoclave process, a married molding process, a tube rolling process and a process oven curing / vacuum pressure.
    [0061] In another embodiment, a metal coated mat according to the embodiments of the invention can be applied as a surface layer to a plurality of stacked sheets (lamination) to form a laminate with conductive properties. FIG. 4 illustrates lamination of a plurality of sheets and a non-woven metal-coated mat according to an embodiment of the invention in the process of being assembled for a vacuum bag process. As shown, a lamination 400 comprised of a metal-coated blanket 402 positioned as a first layer adjacent to a plurality of cloth sheets 404. Cloth sheets 404 can be unidirectional, woven or multi-axial (i.e., unfolded cloths ) and can be positioned in a unidirectional, almost isotropic or orthotropic orientation as known to a person of ordinary skill in the art. The 402 coated metal blanket can be any form of
    Petition 870190100933, of 10/8/2019, p. 33/77
    26/28 realization as previously described. The cloth sheet can be made of fiberglass, carbon, aramid fibers or any other suitable fiber. [0062] Lamination 400 can be positioned in a mold or tool 406 in which the surface of tool 406 is pre-prepared by positioning adhesive tape 408 around a periphery thereof, a gasket felt 410 (for example, felt Armalon®) and a boat cloth 412 over it. Fiberglass filament 414 can be positioned to define an edge of a silicon barrier 416. A resin film 418 such as fluorinated ethylene-propylene copolymer (FEP) can be positioned on lamination 400 followed by a pressure plate 420, one or more layers of fiberglass 422 and sealed by a vacuum bag 424. The system is in communication with one or more holes, such as vacuum hole 426. Pressure and heat is applied to it to cure the finished multifunctional pre-impregnated plates thus forming a laminated panel with global conductivity and intensified stiffness and resistance.
    [0063] In an alternative embodiment, a metal-coated cloth according to the embodiments of the invention can be used to manufacture a conductive prepreg without the use of blankets. According to this embodiment, the cloth or sheet coated with metal, can be positioned in a lamination as described with reference to FIGS. 3 or 4 but without the interleaved blankets coated with metal and / or blanket covered with metal positioned on the surface. It is envisaged that the resulting prepreg will have the same or substantially the same characteristics as the resulting prepregs manufactured according to those described in FIGS. 3 or 4. That is, the resulting prepregs manufactured with one or more metal-coated cloth sheets are expected to exhibit characteristics of overall conductivity as well as intensified stiffness and lightning resistance without the need to interlay blankets
    Petition 870190100933, of 10/8/2019, p. 34/77
    27/28 coated with metal.
    [0064] In another embodiment, a metal-coated mat according to the embodiments of the invention can be combined with an adhesive to form a conductive adhesive. In accordance with this embodiment, the metal-coated mat serves as a carrier for the adhesive. Loaders can provide integrity in handling, flow control during curing, increase adhesive strength and control the thickness of the bonding line. In accordance with this embodiment, the metal-coated mat would function as a carrier for the adhesive to, among other benefits, provide the radius drop protection attributable to the conductivity of the finished adhesive film carrier. Materials that can comprise the adhesive include, but are not limited to, epoxy, bismaleimide, phenolics, cyanate ester, polyimide, combinations thereof and any other similar material.
    [0065] In another embodiment, a metal coated mat according to the embodiments of the invention can be combined with a surface forming film to form a conductive surface forming film. According to this embodiment, the metal-coated mat serves as a carrier for the surface forming film. According to this embodiment, the metal-coated mat would function as a charger for the surface forming film to, among other benefits, provide protection against the radius drop attributable to the conductivity of the finished surface forming film charger. Materials that can comprise the surface forming film include materials that are ultra-low in volatiles and include advantageous properties related to gel, flow, draping, cyclic durability and paintability.
    [0066] In another embodiment, a blanket coated with metal
    Petition 870190100933, of 10/8/2019, p. 35/77
    28/28 or cloth according to the embodiments of the invention can be impregnated with a resin to form a hardened conductive mat or cloth. The resin may include, but is not limited to, epoxy, polyimide, organic resins. A processing method such as solution coated process, hot melt process or any other suitable process can be used to impregnate the metal coated mat, processes which are known to a person of ordinary skill in the art.
    [0067] Component parts manufactured with composites combined with blankets or cloths coated with metal according to the embodiments of the invention can be used in the manufacture of any aerospace component including those in commercial, military, business or regional jet, helicopter and engines jet that requires the composite to have conductive properties. These would include, aircraft structure in the lightning strike areas defined by the FAA (Zones 1A-1C, 2A-2B, 3), for example, wings, fuselages; and aircraft structure that requires protection from potentially harmful electrical events such as electrostatic discharge (ESD), static charge formation, electromagnetic interference (EMI), wing edge glow potential, current return network (CRN) and related fields high intensity (HIRF).
    [0068] Although certain exemplary embodiments were described and shown in the accompanying drawings, it should be understood that such embodiments are merely illustrative of and not restrictive in the broad invention, and that this invention should not be limited to the specific constructions and arrangements shown and described, since several other modifications can occur for those ordinarily skilled in the art.
    权利要求:
    Claims (12)
    [1]
    1. Composite article, characterized by the fact that it comprises:
    a plurality of fibrous reinforcement sheets impregnated with a resin, each sheet adjacent to at least one other sheet; and at least one non-woven mat having a continuous layer of metal or metallic alloy coated on at least one side thereof and contiguous to at least one plate, wherein said layer of metal or metallic alloy has a thickness between 0.1 pm and 25 pm and a lower area weight of 50 g / m 2 and wherein said mat nonwoven is comprised of carbon fibers, fiberglass fibers, aramid fibers, fibers of para-aramid, thermoplastic fibers, or combination thereof, and in which the fibrous reinforcement is made from fibers selected from the group consisting of aramid fibers based on polyphenylene terephthalamide, fiberglass, quartz, carbon and graphite.
    [2]
    2. Composite article according to claim 1, characterized by the fact that each plate is unidirectional.
    [3]
    3. Manufacturing process to manufacture a laminated panel, characterized by the fact that it comprises:
    providing a sheet material comprised of carbon fibers, fiberglass fibers, aramid fibers, para-aramid fibers, thermoplastic fibers, or a combination thereof;
    forming a continuous coating layer of metal or metal beam on at least one side of said sheet material by a coating process selected from the group consisting of: physical vapor deposition; atomic layer deposition, chemical vapor deposition, low pressure chemical vapor deposition and enhanced chemical vapor deposition
    Petition 870190100933, of 10/8/2019, p. 37/77
    2/3 with plasma, where the coated sheet material has a thickness between 0.1 pm and 25 pm and an area weight less than 50 g / m 2 ;
    positioning at least one fibrous reinforcement sheet impregnated with a resin contiguous to the coated sheet material; wherein the fibrous reinforcement is made from fibers selected from the group consisting of aramid fibers based on poly-paraphenylene terephthalamide, glass fiber, quartz, carbon and graphite; and applying pressure and heat to the coated sheet material and at least one sheet to form a laminated panel.
    [4]
    4. Manufacturing process according to claim 3, characterized in that it additionally comprises positioning a plurality of additional fibrous reinforcement sheets impregnated with a resin on the sheet next to the coated sheet material.
    [5]
    Manufacturing process according to claim 3, characterized in that it additionally comprises inserting a plurality of sheet materials coated with a plurality of fibrous reinforcement sheets impregnated with a resin before applying pressure and heat.
    [6]
    6. Manufacturing process according to claim 3, characterized by the fact that at least one plate is unidirectional.
    [7]
    7. Manufacturing process according to claim 3, characterized by the fact that the metal or the metal beam is one of aluminum, copper, silver, nickel, palladium, tin, gold or a combination thereof.
    [8]
    8. Manufacturing process according to claim 3, characterized by the fact that the resin that impregnates the fibrous reinforcement is selected from epoxy, bismaleimide, phenolic compound, cyanate ester and polyimide.
    [9]
    9. Manufacturing process according to claim 3,
    Petition 870190100933, of 10/8/2019, p. 38/77
    3/3 characterized by the fact that the coating layer of metal or metal alloy has a thickness between 0.5 pm and 2 pm.
    [10]
    10. Manufacturing process according to claim 3, characterized by the fact that the area weight of the metal or metal alloy is less than 5 g / m 2 .
    [11]
    11. Manufacturing process according to claim 3, characterized by the fact that the sheet material is one of a woven cloth or a non-woven blanket.
    [12]
    12. Laminated panel, characterized in that it is formed as defined in any of claims 3 to 11.
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    同族专利:
    公开号 | 公开日
    EP2512800B1|2019-11-27|
    US9962907B2|2018-05-08|
    KR20120099275A|2012-09-07|
    EP2512800A1|2012-10-24|
    JP2013514210A|2013-04-25|
    US20110159764A1|2011-06-30|
    CN102905888B|2016-03-09|
    TW201144055A|2011-12-16|
    WO2011075344A1|2011-06-23|
    ES2773041T3|2020-07-09|
    CN102905888A|2013-01-30|
    BR112012013754A2|2016-03-22|
    CA2784656A1|2011-06-23|
    AU2010332128A1|2012-07-26|
    JP5669860B2|2015-02-18|
    AU2010332128A8|2012-08-23|
    AU2010332128B2|2013-10-17|
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    法律状态:
    2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-04-24| B06T| Formal requirements before examination|
    2019-07-16| B07A| Technical examination (opinion): publication of technical examination (opinion)|
    2019-11-26| B09A| Decision: intention to grant|
    2019-12-24| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 07/12/2010, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US28803009P| true| 2009-12-18|2009-12-18|
    PCT/US2010/059219|WO2011075344A1|2009-12-18|2010-12-07|Methods of imparting conductivity to materials used in composite article fabrication & materials thereof|
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