• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
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  • 优先权
    • 专利摘要:
    curable composite material, curable composite laminate, method for making a composite structure, and, structural preform adapted for resin infusion. a composite material including a layer of reinforcing fibers impregnated with a curable resin matrix and a plurality of electrically conductive composite particles adjacent or in proximity to the reinforcing fibers. each of the electrically conductive composite particles is composed of a conductive component and a polymeric component, wherein the polymeric component includes one or more polymers that are initially in a solid phase and are substantially insoluble in the curable resin, but are capable of suffering hair less transition from a partial phase to a fluid phase during a composite material cure cycle.
    公开号:BR112014025708B1
    申请号:R112014025708-6
    申请日:2013-04-15
    公开日:2021-07-20
    发明作者:Carmelo Luca Restuccio；Emiliano Frulloni；Fiorenzo Lenzi
    申请人:Cytec Technology Corp.；
    IPC主号:
    专利说明:

    FUNDAMENTALS
    [0001] In the aerospace industry, the use of composites is increasingly important as a large number of primary and secondary structures in aircraft structures being made of composite materials. The advantages of composites in aircraft designs include a high strength-to-weight ratio, excellent fatigue strength, corrosion resistance and flexibility, which allows for a significant reduction in components and the need for fasteners and joints. However, the application of these materials to primary and secondary structures of modern aircraft presents special challenges due to the dielectric nature of the resin matrix. Although the use of carbon fibers as reinforcement fibers in composite materials can provide some degree of electrical conductivity along their longitudinal direction, due to their graphite nature, the dielectric properties of matrix resins in composite materials reduce the total electrical conductivity of composite materials and structures. Composites with electrically increased conductivity are required for aircraft primary structures to meet the stringent requirements for lightning protection, discharge potential, electrical ground and electromagnetic shielding.
    [0002] The electrical conductivity of resins and composites can be improved by incorporating different conductive particles or polymers in the resin matrix, or in the interlaminar regions of composite structures. Such prior art materials solutions can be used to improve the z-direction conductivity of a composite, but not its mechanical performance. The "z direction" refers to the direction perpendicular to the planes in which the reinforcing fibers are disposed in a composite structure or the axis along the thickness of the composite structure.
    [0003] EP0014104 discloses a prepreg material comprising a resin impregnated fabric net woven from a multiplicity of elongated fiber bundles arranged to cover substantially the entire surface of the net. The individual fibers in the bundles are constructed of a dielectric material and at least some of the individual fibers in at least some of the bundles have an electrically conductive surface coating that extends over substantially the entire length of such fibers. An uncured curable resin impregnates the mesh to form a prepreg material that can be transformed after curing the resin into a rigid article exhibiting conductivity provided by the conductive coating.
    [0004] US 2005/271838 discloses vehicle fuel system components formed from conductively loaded resin-based materials comprising micron conductive powder(s), conductive fiber(s) or a combination of powder conductor and conductive fibers in a base resin host.
    [0005] The document US5009927 describes that a thin film of an electrically conductive material (16) is applied to form an electrically conductive surface (22) on a surface (18) of a polymer coated fabric (14). The method involves coating a woven fiberglass fabric (14) with a polymer solution (6), curing the polymer solution in the fiberglass fabric and then depositing the electrically conductive material onto the surface of the fabric. polymer cured, typically by a sputter technique, to form a flexible, electrically conductive fabric (24). This method helps ensure that when electrically conductive material is applied, the electrically conductive surface formed is continuous and has a controlled, usually constant, thickness. Substantial continuity of the electrically conductive surface is maintained even when the electrically conductive fabric is flexed during subsequent manufacturing operations. Document US2011163275 discloses a resin material comprising at least one thermosetting resin, carbon conductive additive material and at least one resin of thermoplastic polymer. The thermoplastic polymer resin dissolves in the thermosetting polymer resin and the phase separates after curing. A method of making the resin material and additionally a composite material comprising said resin material in combination with a fiber reinforcement is also provided. The resin material and the composite material can be used in an uncured or cured form and can find particular use as a prepreg material.
    [0006] The document US2011287246 discloses a prepreg containing a carbon fiber [A] and a thermosetting resin [B] and, in addition, satisfying at least one of the following (1) and (2). (1) a thermoplastic resin particle or fiber [C] and a conductive particle or fiber [D] are contained, and the ratio by weight expressed by [composite amount of [C] (parts by weight)] / [composite amount of [D] (parts by weight)] is from 1 to 1000. (2) a conductive particle or fiber containing a thermoplastic resin core or core coated with a conductive substance [E].
    [0007] WO2011075344 describes embodiments of the invention directed to sheet materials coated with metal or metal alloy including, but not limited to, fabrics and webs having a metal content between one (1) and fifty (50) grams per square meter (g / m2). Metal coated sheet materials can be used as is or in conjunction with prepregs, adhesives or surface films to provide lightning protection (LSP) and/or bulk conductivity, among other benefits, to the resulting composite article. In one embodiment, the metal-coated sheet material is impregnated with a resin. In accordance with embodiments of the invention, a metal is applied to one or both sides of the fabric or web by a physical vapor deposition coating process. The resulting metal coated fabric or web can be used as a carrier in surface films to impart surface conductivity; can be used as a carrier in adhesives to form conductive adhesive joints; can be interspersed (one or more coated metal webs) between prepreg layers to impart surface and/or bulk conductivity as well as strength; or can be used to manufacture composite articles. SUMMARY
    [0008] The present description refers to composite materials reinforced with fibers, which can provide high conductivity in the thickness direction, as well as improving the properties of impact resistance and delamination. In accordance with an embodiment of the present description, the fiber reinforced composite material includes: a. at least one fiber reinforcing structural layer impregnated with a curable resin matrix; and b. at least one electrically conductive composite particle adjacent or in proximity to the reinforcing fibers.
    [0009] The electrically conductive composite particle is a micron-sized particle composed of at least one electrically conductive material dispersed in a polymeric material. As such, each conductive composite particle has a conductive component and a polymeric component. The polymer component of the electrically conductive composite particles is initially in a solid phase and substantially insoluble in the curable resin matrix prior to curing the resin matrix, but is capable of at least one phase transition to a fluid phase during the cycle. of resin matrix curing. The curable resin matrix of the structural layer can be a hardenable composition, wherein the polymeric component of the conductive composite particle is at least partially soluble during the resin matrix curing cycle.
    [0010] A method for fabricating a multilayer composite structure having composite particles in interlaminar regions is also disclosed.
    [0011] Another aspect of the present description is directed to conductive polymeric fibers and non-woven structures, with properties similar to composite particles. BRIEF DESCRIPTION OF THE DRAWINGS
    [0012] Fig. 1 schematically represents an electrically conductive composite particle according to an embodiment of the present disclosure.
    [0013] Fig. 2 illustrates an exemplary process for producing electrically conductive composite particles.
    [0014] Fig. 3A schematically illustrates a composite structure containing electrically conductive particles in interlaminar regions before curing.
    [0015] Fig. 3B schematically illustrates the structure of the composite depicted in FIG. 2A after curing.
    [0016] Fig. 4 is a scanning electron microscope (SEM) image showing micron-sized conductive composite particles fabricated in accordance with an example of the present disclosure.
    [0017] FIGS. 5A and 5B are two micrographs showing cross-sectional views of a composite structure cured based on the incorporation of copper/polyamide composite particles in the interlaminar region.
    [0018] Fig. 6 is a micrograph showing a cross section of a cured composite structure based on the incorporation of conductive copper/PES particles in the interlaminar region. DETAILED DESCRIPTION
    [0019] "Third generation composite materials" have recently been developed for primary structures in aerospace applications. The impact resistance of such materials is improved by a polymeric intercalated alternation between layers of reinforced fibers. The presence of interlaminar polymer particles, fibers or films can significantly reduce the electrical conductivity in the “z direction” of the fiber reinforced composite material, due to the dielectric nature of the materials. Therefore, it is necessary to improve the z-direction electrical conductivity of composites in "third generation materials" to ensure acceptable levels of potential discharge and electrical grounding to avoid possible catastrophic failure of composite components or accidents associated with fuel vapor ignition and explosions of later fuel tanks after a lightning event.
    [0020] The electrical conductivity of resin-based composite materials can be improved by incorporating different conductive particles or polymers in the resin matrix, or in the interlaminar regions of composites of various layers and structures. Metal fillers can be used at high loads (generally greater than 50% by weight) to reduce resin resistivity, but this approach typically results in significant weight gain and substantial reductions in mechanical properties. Conjugated conductive polymers can improve resin system conductivity at relatively low loads, but they jeopardize the thermomechanical performance of structural and pre-impregnated resin systems for aerospace applications. Carbon-based additives such as carbon black, carbon nanotubes, carbon nanofibers can also be used to modify the composition of resin systems, but they have process capacity and dispersion difficulties, thus limiting their use in advanced composite structures.
    [0021] A series of interlaminar particles having a conductive coating was recently proposed as a solution to create an electrical bridge between two adjacent layers. However, these conductive particles can usually only provide high electrical conductivity or impact resistance properties, but not both.
    [0022] The present disclosure provides a multifunctional solution that includes a composite material that has one or more fiber structural reinforcement layers impregnated with a curable resin matrix and electrically conductive composite particles, with the hardening capabilities. Furthermore, when such composite particles are used in the interlaminar regions of multilayer composite structures, they are capable of creating electrical bridges between the structural fiber layers in the multilayer composite structures. The solution of the present disclosure provides not only improved z-direction conductivity of composite structures, but also improved mechanical properties such as interlaminar fracture hardness and impact strength. The term "conductive composite particle" will be used hereinafter to designate "electrically conductive composite particles". Conductive composite particles are micron-sized particles composed of at least one electrically conductive material dispersed in at least one polymeric material. As such, each electrically conductive composite particle has an electrically conductive component and a polymeric component.
    [0023] When a plurality of composite materials are stacked in a multilayer configuration (i.e., a backing) and cured, the polymer component of the composite particles dissolves in the resin matrix of the structural layers, thereby releasing the conductive component , which in turn creates a controlled interlaminar region and a conducting bridge between the fiber layers. This material solution can simultaneously improve the impact resistance and delamination resistance of the multilayer composite structure by spreading out or dissipating electrical current, such as those generated by lightning, over a larger area of the structure. composite, thus reducing the likelihood of catastrophic damage to localized portions. Furthermore, composite particles can potentially be an effective solution to mitigate or eliminate the direct effect of lightning and, in particular, the edge glow phenomenon in third generation composite structures. Finally, electrically conductive composite particles can provide additional benefits in terms of composite electromagnetic performance. Composite particles based on highly conductive and/or magnetic fillers can be used as a flexible tool to adjust the electromagnetic interference (EMI) of shielding efficiency, permittivity properties and magnetic permeability of composite structures. Conductive composite particles
    [0024] Fig. 1 schematically represents a conductive composite particle according to an embodiment of the present disclosure. Although FIG. 1 shows a spherical shaped particle, it is to be understood that the electrically conductive composite particles of the present disclosure are discrete, three-dimensional structures which may be of any suitable shape, including, but not limited to, spherical, spheroidal, ellipsoidal, cubic, polyhedral shape , rod shape, disc shape, and so on. Also, particles can have a well-defined geometry, or they can be irregular in shape.
    [0025] The average particle size (d50) of conductive composite particles is less than 150 µm, preferably within the range of 10-90 µm, more preferably within the range of 10-60 µm. The d50 represents the mean of the particle size distribution, or, alternatively, is the value of the distribution such that 50% of the particles have a particle size of that value or less.
    [0026] The conductive component of the conductive composite particle may include metallic materials, non-metallic conductive materials, and combinations thereof, having an electrical conductivity greater than 1 x 103S/m. Suitable metallic materials include any known metals, including, but not limited to, silver, gold, platinum, palladium, nickel, copper, lead, tin, aluminum, titanium, alloys and mixtures thereof. Preferably, metallic materials have an electrical conductivity greater than 1 x 107S/m, more preferably greater than 3 x 107S/m. suitable non-metallic conductive materials include, but are not limited to, carbon or graphite based materials.
    [0027] When the conductive material is metallic, the conductive component is present in the range of 1% to 90% by weight based on the total weight of the conductive composite particle, preferably within the range of 30% to 85% by weight, and more preferably, in a 50% to 80% range. When the conductive material is non-metallic or carbon based, the conductive component is present in the range of 1% to 75% by weight based on the total weight of the conductive composite particle, preferably in the range of 1% to 25% by weight .
    [0028] The polymer component of the composite particles may include one or more polymers that are initially in a solid phase and substantially insoluble in a curable resin matrix (e.g., host resin matrix) at room temperature (i.e., 20° C - 25°C) or under conditions not sufficient for complete cure of the matrix resin, but is capable of undergoing at least a partial phase transition to a fluid phase during the curing cycle of the host resin matrix. During the cure cycle, the polymer component dissolves in the resin matrix in contact with the resin matrix. In other words, the polymeric component is a material that has no solubility (or negligible solubility) in the curable resin matrix at room temperature or under conditions not sufficient for complete curing of the resin matrix (eg, during pre-fabrication. impregnated), while its solubility is substantial (ie greater than 50% dissolves) or total (ie dissolves completely) during the resin matrix curing cycle.
    [0029] As used herein, the term "cure" or "cure" refers to the hardening of a resin matrix by crosslinking polymer chains, caused by chemical additives, ultraviolet radiation, microwave radiation, electron beams , gamma or other radiation, or thermal radiation or non-thermal radiation.
    [0030] The solubility properties of polymers for the polymer component in the host curable resin matrix, as discussed in this context, can be determined by several known methods, including optical microscopy, spectroscopy, and the like.
    [0031] For a material to be soluble in another material, the difference in its solubility parameters (Δδ) must be as small as possible. The solubility parameter for a polymer can be determined by a calculation based on the group contribution method described by Van Krevelen (see DW Van Krevelen, Properties of Polymers, 3rd Revised Edition, Elsevier Scientific Publishing, Amsterdam, 1990, Chapter 7, pp 189-224).
    [0032] The solubility parameter of a polymer can also be determined using the Hansen solubility parameters (HSP), as a way to predict whether one material dissolves into another to form a solution. Hansen's parameters are based on the idea that “like dissolves like”, where one molecule is defined as being “like” another if it binds in a similar way.
    [0033] Suitable polymers for the polymeric component of the conductive composite particle can be selected from homopolymers or copolymers of functionalized or non-functionalized thermoplastic resins, alone or in combination with thermosetting resins. Suitable thermoplastic materials may include, by way of example, one of the following characteristics, alone or in combination: polyurethanes, polyketones, polyamides, polyphthalamides, polystyrenes, polybutadienes, polyacrylates, acrylics, polymethacrylates, polyethersulfone (PES), polyetherethersulfone (PEES), sulfones , poly, polyesters, liquid crystal polymers, polyimides, polyetherimides (PEI), polyetherketones (PEKK), polyetherketones (PEEK), polyarylethers, polyarylsulfides, polyphenylenes, polyphenylene oxide (PPO), polyethylene oxide (PEO), polypropylene oxide . Suitable polymers can also include elastomers (including segmented elastomers), or a combination of a thermoplastic polymer and the elastomeric polymer.
    [0034] Preferably, the polymer component is selected from functionalized thermoplastic polymers that are miscible with suitable thermosetting matrices, have a high modulus and glass transition temperature (Tg), and are rigid. In general, thermoplastic polymers with a Tg of at least 150°C, preferably greater than 200°C, are suitable.
    [0035] The number average molecular weight of thermoplastic polymers can be in the range of 2,000 to 60,000. Preferably it is more than 9,000, for example 11,000 to 25,000. The presence of these thermoplastic polymers in a host thermosetting resin increases the hardness of the cured thermosetting resin, providing resistant thermoplastic zones between crosslinked thermosetting zones. The functionalized thermoplastic polymer preferably contains pendant or chain terminating functional groups which will chemically react with the functional groups in the thermosetting resin composition to form covalent, ionic or hydrogen bonds. These functional groups can be obtained by a monomer reaction or by subsequent conversion of the resulting polymer before or after isolation. Preferably, the functional groups of the thermoplastic polymer are of the formula: -A-Y
    [0036] When A is a bivalent hydrocarbon group, preferably aromatic, and Y are groups that provide active hydrogen, in particular OH, NH2, NHR' or SH, where R' is a hydrocarbon group containing up to 8 carbon atoms, or provide other crosslinking reactivity especially epoxy, (meth)acrylate, cyanate, isocyanate, acetylene, ethylene vinyl, allyl, benzoxazine, anhydride, oxazoline, maleimide and saturation containing monomers.
    [0037] The polymeric component of the conductive composite particle is adapted to undergo partial or complete transition phase, e.g. it may completely dissolve, or it may partially dissolve. "Partially dissolve" means that a portion of the polymer component is dissolved in the matrix, while another portion retains its elemental or original form. Partial dissolution can be achieved by ensuring that the acquisition time and temperature are insufficient for complete dissolution or by providing the polymer component as a blend or copolymer with one or more insoluble polymers, for example, in the form of a random copolymer or as a block, or as a mixture with one or a derivative of organic or inorganic compounds.
    [0038] In another embodiment, the polymer component may comprise a mixture of thermoplastics and one or more thermosetting resins, and optionally one or more curing agents and/or catalysts for the thermosetting resins. Suitable thermosetting materials may include, among others, epoxy resins, an addition polymerization resin, especially bismaleimide resins, acrylics, unsaturated polyesters, vinyl ester resins, cyanate ester resins, isocyanate modified epoxy resins, resins phenolics, benzoxazine resins, formaldehyde condensation resins (as with urea, melamine or phenol), polyesters, acrylics, reaction products and combinations thereof. Methods of Preparing Conductive Composite Particles
    [0039] The conductive composite particles of the present disclosure can be manufactured according to a single or multi-step process. In one embodiment, particles are manufactured by a two-step process that includes an initial high-shear manipulation step to disperse the conductive component into a polymeric material, followed by a particle size reduction step. An exemplary method for producing composite particles is illustrated in FIG. 2. A conductive material 31 and a polymeric material 32 are manipulated in an extruder 33 to form pellets. It should be understood that the "conductive material" can include one or more conductive materials, and the "polymeric material" can include one or more polymers. In such an embodiment, the polymeric material and the conductive material can be fed to the extruder, simultaneously or sequentially, so as to preferably form a homogeneous physical mixture of the conductive material and polymer. The polymeric starting material 32 to be introduced into the extruder can be in an amorphous phase, or in the form of a melt.
    [0040] The conductive starting material for preparing the particles can be selected from known metals, including, but not limited to, silver, gold, platinum, palladium, nickel, copper, lead, tin, aluminum, titanium, alloys and their mixtures. Furthermore, the conductive starting material can be of any suitable shape and morphology, such as flakes, powders, fibers, spheres, disks, dendrites or any other three-dimensional shape with a micrometer or nanometer dimension, alone or in combination. Preferably, the conductive starting material has a high specific surface area and low bulk density. The conductive component preferably has a bulk density (AD) of less than 2.0 g/cm3, and the specific surface area (SSA) is preferably greater than 0.1 m2/g. Examples of suitable metallic materials are 525 low density nickel flakes (AD = 0.65 g/cm3, available from Novamet Specialty Products Corp. USA), silver powder CAP 9 (SSA = 3.0 m2/g, available from Johnson Matthey, UK), FS34 silver flakes (SSA = 1.2 m2/g, available from Johnson Matthey, UK) and CH-L7 copper granulate (AD = 0.6-0.7 g/cm3, SSA = 0.23 m2/g, available from GGP Metalpowder AG, Germany).
    [0041] The conductive starting material to prepare the particles can also be selected from carbon or graphite materials, such as chopped and short carbon fibers, graphite flakes, graphite nanoplates, carbon black, carbon nanotubes single-walled carbon nanotubes (SWCNT), double-walled carbon nanotubes (DWCNT), multi-walled carbon nanotubes (MWCNT), carbon nanofibers, carbon nanospheres, carbon nanorods, fullerenes, carbon nanostrings, carbon nanoribbons carbon, carbon nanofibrils, carbon nanoneedles, carbon nanosheets, graphenes, carbon nanocones, carbon nanorollers (roller-like forms), as well as the corresponding boron nitride products thereof, with and without conductive coating. These "nano" structures refer to structures that have smaller diameters or dimensions less than 1 micron.
    [0042] The conductive starting material can also be selected from coated products. Coated products include core structures having an organic or inorganic core, which may be conductive or non-conductive shells, and one or more conductive shells. Suitable metal coated products include, but are not limited to, metal coated graphite flakes, metal coated polymers, metal coated fibers, metal coated ceramics, metal coated glass, metal coated hollow glass spheres, carbon coated glass, carbon-coated polymers, carbon-coated fibers and carbon-coated ceramics.
    [0043] Examples of non-metallic conductive materials are NC7000 multi-walled carbon nanotubes (available from Nanocyl, Belgium), 3775 micrometer graphite flakes (SSA = 23.7 m2/g, available from Asbury Graphite Mills , Inc., USA), 4012 micron synthetic graphite flakes (SSA = 1.5 m 2 /g, available from Asbury Graphite Mills, Inc., USA). Examples of the coated products are nickel-coated graphite flakes from Novamet Specialty Products Corp, USA (AD = 1.7 g/cm3 - 1.9 g/cm3).
    [0044] The temperature inside the extruder must be controlled for better rheology of the composition inside the extruder, for the type and amount of conductive material added. In a preferred embodiment, the temperature profile ranges from about 90°C to about 350°C. A temperature profile can be used along the length of the extruder. Optionally, additives, diluents, dispersants, pigments or stabilizers can be added to the conductive polymer/blend to improve stability, processability and dispersion of the conductive material in the polymeric material.
    [0045] The extruder can be equipped with screws having conventional low or high shear/mix profiles or a combination thereof, depending on the type of filling and content, and on the rheological behavior of the polymer. In one embodiment, a sequence of conventional low-shear mixing screw sections can be used to achieve satisfactory dispersion levels. In a preferred embodiment, the extruder is equipped with a high shear screw profile having conventional mixing segments associated with chaotic mixing units in order to create the best balance between shear forces and drum pressure to optimize dispersion levels , and said process conditions can be achieved by using a Prism TS24HC extruder equipped with a 24 mm co-rotating twin screw system with a 40 to 1 LD ratio. feed to suit different materials (conductive material or polymer pellets) can be used. A screw speed of about 200-300 rpm and a specific temperature profile in the various heating zones can be used to obtain a maximum torque of 60% to 95% for a given mixture. It should be understood that other methods can be used to disperse the conductive material into the polymeric material using conventional techniques known to one skilled in the art, such as mechanical agitation, sonication, high shear mixing, rotor stator mixing and sol-gel techniques.
    [0046] The process for producing the composite particles may also include a particle size reduction/micronization step. Micronization can be carried out in accordance with conventional techniques known in the art, for example, rotary impact milling, rotoplex milling (i.e., milling in a Rotoplex mill manufactured by Hosokawa Micron Co., Ltd.), rotary classifier milling, milling by ball, ultra-fine grinding in a counter-rotating pin mill (eg Alpine Contraplex available from Hosokawa Micron Ltd), opposite jet milling in fluid bed, spiral flow jet milling, cryogenic milling. In a preferred embodiment, the pellets from extruder 33 (FIG. 2) are then milled in an Alpine 34 cryogenic milling system equipped with different rotary milling means to produce a micro-sized particle powder having (d50) an average particle size of less than 150 µm, or less than 60 µm in some embodiments.
    [0047] Cryogenic milling is a size reduction process in which the polymer is prepared brittle and subsequently milled in a cryogenic liquid (usually liquid nitrogen or liquid argon) or at a cryogenic temperature. The cryogenic grinding method has been shown to be a cost-effective and energy-efficient method for producing powders with a controlled fine particle size distribution, reducing the risk of thermal damage caused by volatilization or overheating of components. The specific sequence of steps using pin, beater, overhanging beater and beater plate discs are generally designed to achieve micronized particles that exhibit the desired average particle size distribution (d50). Composite Materials and Structures
    [0048] The composite particles of the present disclosure can be used as interlaminar particles between fiber reinforced polymer layers, e.g., pre-impregnated layers. As such, the host resin system in this context is the resin matrix of fiber reinforced polymer layers or pre-impregnated layers.
    [0049] The host resin matrix can be a hardenable/thermosetting composition, in which the polymeric component of the conductive composite particle is at least partially soluble, during the cure cycle, in which the phase transition to the fluid phase occurs by dissolving the resin matrix polymer component. Initially, when the conductive composite particles are in contact with or dispersed in the host resin matrix during mixing or during the pre-impregnated manufacturing process, the composite particles are in a solid phase, and are insoluble in the host resin matrix . During the composite material/resin matrix curing cycle, the polymer component of each composite particle substantially or completely dissolves in the host resin matrix, thereby releasing the conductive component as distinct, free-flowing structures in the interlaminar region of the composite . It should be understood that, in some cases, the polymer component may not completely dissolve after curing (but dissolve substantially), and therefore, the conductive component may be bonded to a small fragment of insoluble polymeric material. In some embodiments, the separation step between the polymer component and the host resin matrix occurs during the cure cycle of the host resin matrix.
    [0050] The host resin matrix (or resin system), in which the polymeric component of the composite particles is soluble during curing, may contain one or more uncured thermosetting resins, which include, among others, epoxy resins , bismaleimide resins, vinyl ester resins, cyanate ester resins, isocyanate modified epoxy resins, phenolic resins, benzoxazine, formaldehyde condensed resins (as with urea, melamine or phenol), polyesters, acrylics and combinations thereof. In one embodiment, the host resin matrix is a thermosetting composition, in which at least 50% of the polymeric component of the conductive composite particle is soluble during curing of the resin matrix.
    [0051] Suitable epoxy resins include polyglycidyl aromatic diamine derivatives, monoaromatic primary amines, aminophenols, polyhydric phenols, polyalcohols, polycarboxylic acids. Examples of suitable epoxy resins include polyglycidyl ethers of bisphenols such as bisphenol A, bisphenol F, bisphenol S and bisphenol K; and polyglycidyl ethers of cresol and phenol-based novolacs.
    [0052] Specific examples are tetraglycidyl derivatives of 4,4'-diaminodiphenylmethane (TGDDM), diglycidyl ether of resorcinol, triglycidyl-p-aminophenol, triglycidyl-m-aminophenol, diglycidyl ether bromobisphenol F, tetraglycidyl derivatives of diaminodiphenylmethane, triglycidyl ether of trihydroxyphenyl methane, polyglycidyl ether of phenol-formaldehyde novolac, polyglycidyl ether of o-cresol novolac or tetraglycidyl ether of tetraphenylethane.
    Commercially available epoxy resins suitable for use in the host resin matrix include N,N,N',N'-tetraglycidyl diamino diphenylmethane (e.g. MY 9663, MY 720 and MY 721 by Huntsman); N,N,N',N'-tetraglycidyl-bis(4-aminophenyl)-1,4-diiso-propylbenzene (e.g. EPON 1071 from Momentive); N,N,N',N'-tetralicidyl-bis(4-amino-3,5-dimethylphenyl)-1,4-diisopropylbenzene, (for example EPON 1072 from Momentive); triglycidyl ethers of p-aminophenol (eg MY 0510 from Hunstman); m-aminophenol triglycidyl ethers (eg MY 0610 from Hunstman); diglycidyl ethers of bisphenol A based materials such as 2,2-bis (4,4'-dihydroxy phenyl) propane (eg DER 661 from Dow, or EPON 828 from Momentive, and Novolac resins preferably viscosity 8 -20 Pa.s at 25°C, glycidyl ethers of phenol Novolac resins (eg DEN 431 or DEN 438 from Dow); phenolic novolac based on di-cyclopentadiene (eg Tactix 556 from Huntsman); -phthalate (eg GLY CEL A-100); diglycidyl derivative of dihydroxy diphenyl methane (Bisphenol F) (eg PY 306 from Huntsman) Other epoxy resins include cycloaliphatic such as 3',4'-epoxycyclohexyl-3,4 -epoxycyclohexane carboxylate (eg CY 179 from Huntsman).
    [0054] In general, the host resin matrix contains one or more thermosetting resins in combination with other additives such as curing agents, curing catalysts, comonomers, rheology control agents, viscosity agents, inorganic fillers or organics, elastomeric hardening agents, core hardening particles, stabilizers, inhibitors, dyes, pigments, flame retardants, reactive diluents, soluble or particulate thermoplastics and other additives well known to those skilled in the art to modify the properties of the resin before or after curing.
    [0055] The addition of the curing agents and/or catalysts in the host resin matrix is optional, but the use of these can increase the cure rate and/or reduce the curing temperatures, if desired. The curing agent is suitably selected from known curing agents, for example aromatic or aliphatic amines or guanidine derivatives. An aromatic amine curing agent is preferably an aromatic amine having at least two amino groups per molecule, and diaminodiphenyl sulfones are particularly preferred, for example, where the amine groups are in the meta or para positions with respect to the sulfone group. Particular examples are 3,3'- and 4,4'-diaminodiphenylsulfone (DDS); methylenedianiline; bis(4-amino-3,5-dimethylphenyl)-1,4-diisopropylbenzene; bis(4-aminophenyl)-1,4-diisopropylbenzene; 4,4'methylenebis-(2,6-diethyl) aniline (MDEA from Lonza); 4,4'methylenebis-(3-chloro,2,6-diethyl)-aniline (MCDEA from Lonza); 4,4'methylenebis(2,6-diisopropyl)-aniline (M-DIPA from Lonza); 3,5-diethyl-toluene-2,4/2,6-diamine (D-ETDA 80 from Lonza); 4,4'methylenebis-(2-isopropyl-6-methyl)-aniline (M-MIPA from Lonza); 4-chlorophenyl-N,N-dimethyl-urea (for example Monuron); 3,4-dichlorophenyl-N,N-dimethyl-urea (eg Diuron™) and dicyandiamide (eg Amicure™ GC 1200 from Pacific Anchor Chemical).
    [0056] Bisphenol chain extenders such as bisphenol-S or thiodiphenol are also useful as curing agents for epoxy resins. Examples are 3.3’- and 4.4’-DDS.
    Suitable curing agents include anhydrides, particularly polycarboxylic anhydrides, such as nadic anhydride, methylnadic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, and trime anhydride.
    [0058] FIGS. 3A and 3B illustrate an embodiment in which composite particles are incorporated into a composite structure. Referring to FIG. 3A, a plurality of conductive particles 20 are composites dispersed in the interlaminar regions 21, 22 formed between the layers of curable composites, 23, 24, 25. Each of the composite particles 20 contains a mixture of a metallic material and a polymeric material . Each of the composite layers 23, 24, 25 is composed of reinforcing fibers impregnated with a curable resin matrix (i.e., uncured or not fully cured). The resulting laminated material is then subjected to curing. On curing the stack of composite layers, the polymer component of the conductive composite particles 20 undergoes a partial or complete phase transition to a fluid phase, and completely dissolves or substantially dissolves in the resin matrix of the composite layers 23, 24 , 25, thus releasing the metallic material in the interlaminar region, as depicted in FIG. 3B. When the composite layers 23, 24, 25 contain conductive reinforcing fibers such as carbon fibers, the electrically conductive released metallic material forms bridges between the reinforcing fiber layers in the z direction.
    [0059] The "interlaminar region" refers to the region between adjacent layers of reinforcing fibers in a multilayer composite structure. Each fiber layer is impregnated with one or more polymeric materials. Such a layer may be referred to as "fiber reinforced polymer layer". The fiber reinforced polymer layer may be in the form of a prepreg. The term "prepreg" as used herein includes a sheet or layer of fibers that has been impregnated with a resin matrix over at least a portion of its volume. The prepreg used to manufacture aerospace structures is typically a resin-impregnated sheet of unidirectionally aligned reinforcing fibers, often referred to as "tape" or "unidirectional tape". The resin matrix can be present in a partially cured or uncured state. Prepregs can be fully impregnated prepregs or partially impregnated prepregs. Typically, a prepreg is in a form that is ready for molding and curing into the final composite portion and is used in the fabrication of load-bearing structural components such as the wings, fuselage, bulkheads, and aircraft control surfaces. . The important properties of cured prepregs are high strength and stiffness with reduced weight.
    [0060] A plurality of pre-impregnated layers may be placed above a stacking sequence to form a "pre-impregnated backing". The pre-impregnated layers within the support can be positioned in a selected orientation relative to one another, eg 0°, ± 45°, 90°, etc. Prepeg supports can be manufactured using techniques that may include, but are not limited to, manual support, automated tape support (ATL), advanced fiber placement (AFP), and filament winding.
    [0061] Suitably, the curing of the prepeg composite or support structure is generally carried out at an elevated temperature up to 200°C, preferably in the range of 170°C - 190°C, and with the use of high pressure to prevent the effects deformation of leaking gases, or to prevent the formation of a vacuum, suitably at a pressure of up to 10 bar (1 MPa), preferably in the range of 3 bar (0.3 MPa) to 7 bar (0.7 MPa). Preferably, the curing temperature is reached by heating up to 5°C/minute, for example 2°C/min to 3°C/min and is maintained for the required period of up to 9 hours, preferably up to 6 h, for example, 2 hours to 4 hours. Using a catalyst in the resin matrix can allow for even lower curing temperatures. Pressure is released over, and the temperature is reduced by cooling down to 5°C/min, eg to 3°C/min. Post-cure at temperatures in the range of 190°C to 350°C and atmospheric pressure can be carried out by employing suitable heating rates to improve the glass transition temperature of the resin matrix.
    [0062] For manufacturing high-performance composite materials and pre-impregnated materials, suitable reinforcing fibers can be broadly characterized as having a tensile strength greater than 100,000 psi and a modulus of elasticity greater than two million psi. Fibers useful for these purposes include carbon or graphite fibers, glass fibers and fibers formed from silicon carbide, alumina, titania, boron and the like, as well as fibers formed from organic polymers such as, for example, polyolefins, poly(benzothiazole), poly(benzimidazole), polyarylates, poly(benzoxazole), aromatic polyamides, polyaryl ethers and the like, and can include blends having two or more such fibers. Preferably, the fibers are selected from glass fibers, carbon fibers and aromatic polyamide fibers such as the fibers sold by DuPont under the trade name KEVLAR. The fibers can be used in the form of selectively discontinuous and continuous cracking tows made of multiple filaments, as continuous unidirectional or multidirectional tapes, or as woven, woven, non-crimped, and non-woven fabrics. The fabric shape can be selected from a flat, satin, or twill weaving style. Non-crimped and multi-axis shapes can have a number of fiber layers and orientations.
    [0063] The conductive composite particles are present in a content of 0.1% to 25%, by volume, based on the total resin content in the composite structure, and preferably in the range of 5% to 15%. In certain embodiments, the conductive composite particles can be used in combination with the non-conductive interlaminar stiffening particles. In such embodiments, the combination of conductive and non-conductive particles can be present at a content of up to 25% by volume based on the total resin content of the composite material. Non-conductive interlaminar hardening particles can include functionalized, non-functionalized, or cross-linked elastomeric particles. Suitable materials for the non-conductive particles can be selected from the group consisting of a polyimide material (eg P84), an emulsified poly(phenylene oxide) material (eg EPPO 16), poly material (phenylene oxide) (PPO), carboxy terminated butadiene nitrile (CTBN), polyamide (nylon), poly (ether etherketone) (PEEK). Non-conductive thermoplastic particles can be crosslinked thermoplastic particles, for example, composite particles of crosslinked polyethersulfone (PES), crosslinked polyethersulfone (PEES), crosslinked polyetherimide (PEI), crosslinked polyphenylene oxide (PPO), or a crosslinked copolymer thereof. Fabrication Methods for Composite Materials and Structures
    [0064] The composite materials of the present disclosure can be manufactured using different processes. In general, a method for incorporating the composite particles in making composite materials can include: i. dispersing at least one conductive material in a polymeric material to form a composite mixture; ii. optionally heat treating the composite mixture; iii. forming conductive micron-sized composite particles from the composite mixture; iv. optionally, heat treatment of the micron-sized conductive composite particles; and v. forming a stack of composite materials incorporating the conductive composite particles in at least one interlaminar region between adjacent layers of reinforcing fibers, wherein each composite material includes at least one layer of fiber reinforced polymer, wherein the polymer layer Fiber reinforced is composed of reinforcing fibers, impregnated with a curable resin matrix.
    [0065] In one embodiment, composite particles are deposited onto the surface of a pre-impregnated layer prior to laminating multiple pre-impregnated sheets together to form a laminated stack that is ready to be cured. The composite particles can be deposited by any conventional techniques such as spraying, electrostatic deposition, dispersion coating, spray dispensing, and any other technique known to the person skilled in the art. The distributed composite particles adhere to the pre-impregnated surface due to the adhesion of the resin. When the pre-impregnated layers are stacked together to form a laminated board, the particles remain in the interlaminar regions of the laminated board.
    [0066] In another embodiment, specific amounts of composite particles are mixed with the curable/uncured resin matrix prior to prepreg fabrication. In such an embodiment, resin films are manufactured by first coating a resin mixture containing particles onto a release paper. Then, the resulting resin film is laminated to a fiber layer under the aid of heat and pressure to impregnate the fibers, thus forming a prepreg layer with a specific area fiber weight and resin content. During the lamination process, the composite particles are filtered and remain external to the fiber layer, due to the fact that the particle size is larger than the spacing between the fibers. Subsequently, when two layers of prepregs containing composite particles are laminated on top of each other, the composite particles are positioned in the interlaminar region between two adjacent layers of prepeg. The polymer component of the composite particles has negligible or no solubility under normal prepreg conditions.
    [0067] In an alternative embodiment, a curable resin composition without composite particles is coated onto a release paper to form a resin film, which is then placed in contact with one or both opposing surfaces of a layer of fibers . The resin impregnates the fibers and leaves little or no resin on the outer surfaces of the fiber layer. Subsequently, a second curable resin film containing the composite particles is brought into contact with the outer surface of the resin-impregnated fiber layer. An additional film of curable resin containing the composite particles can be contacted with the outer surface opposite the resin impregnated fiber layer to form a sandwich structure. As a result, a particulate-rich conductive resin layer remains on the outside of the impregnated fiber layer and no longer impregnates the fibers. A plurality of such structures are laminated together to form a composite structure with composite particles in interlaminar regions.
    [0068] In another embodiment, two films of curable resin composition without composite particles are placed in contact with the two opposite surfaces of a layer of fibers. The resin impregnates the fibers and leaves little or no resin on the outer surfaces of the fiber layer. Subsequently, two curable resin films containing composite particles are brought into contact with opposite surfaces of the pre-impregnated fiber layer. A plurality of such structures are laminated together to form a composite structure with composite particles in interlaminar regions. Such an approach is preferred as it tends to provide a well-ordered laminate result from particles that do not disturb fiber positioning.
    [0069] The composite materials, structures or prepregs formed by the above methods can be in the form of tapes, towpregs, or wefts, with continuous or cut lengths. Alternative Modalities
    [0070] According to another aspect of the present disclosure, the mixture of conductive polymeric material and conductive material used to form composite particles, as discussed above, can be used for the manufacture of conductive polymer fibers, non-woven materials and structures (eg, transparent curtain, mat, weft, veil, fleece, fabric, fiber preform, and so on).
    [0071] Conductive polymer fibers can be produced by techniques known in the art for manufacturing synthetic fibers. Preferably, the conductive polymer fibers are obtained by continuous extrusion of polymer/conductor mixtures into coils, followed by mechanical stretching with heating. More preferably, the polymer/conductor mixture in molten form is removed in an elemental form, cooled, then subjected to a regime of heating and mechanical stretching that can guide the polymer chains and generate the conductive composite elastomeric element and predisposed to dissolution. Stretching may include pulling the extruded element into air for a desired distance, for example, 50 to 500 mm. In one embodiment, the polymer/conductor mixture, in the form of pellets or other extrudable form, is fed to an extruder having a die head (or the like), which is provided with a desired number of holes or slots.
    [0072] The fibers can be prepared as multifilaments of up to 20 filaments, which are expelled from the molten polymer/conductive mixture, cooled and optionally twisted as desired, and then subjected to heating and stretching.
    [0073] Conductive polymer fibers can be in the form of yarns with spun yarn monofilaments, extruded yarns, molded yarns, continuous filaments, continuous fibers, bi- or multicomponent fibers, random fibers, stapled fibers, staple fibers, staple fibers , tangled filaments, fibers and hollow filaments, and combinations thereof. The fiber can be either a yarn made up of several monofilaments or single and multiple monofilaments. Furthermore, the fibers can have more complex structures such as sheath/core, side/side, cross-section with bent segment configuration or an islands-in-the-sea configuration, and can be made of different polymers or their blends. . Conductive polymer fibers can contain additional organic or inorganic fillers or modifiers. Preferably, the fiber or yarn comprises fiber filaments each having a diameter of no more than about 100 µm.
    [0074] Conductive non-woven materials formed from conductive polymer fibers can take the form of non-woven fabric mats, wool mats and veils, which can be produced using conventional manufacturing techniques such as wet deposition, carding , air laying, bonding fibers, fusion-blow, fast spinning techniques, electrostatic spinning, water jet drilling and needle punching.
    [0075] In spin bonding, the conductive/polymer blend pellets are fed into an extruder and the molten product is forced through a plurality of orifice plates to form continuous filaments. The filaments are cooled by means of a stream of air in a blow zone, extracted by aerodynamic forces and then transported to the downstream discharge channel. The filaments are deposited onto a wire mesh carrier as a non-woven web of random fibers. This mesh is transferred to a binding calender where heat and pressure are applied to define the final product. After cooling, the weft can be wound.
    [0076] In the melt blowing process, the conductive/polymer mixture in the form of a molten material is extruded through a matrix containing several hundred small holes. Hot air streams exiting the left and right sides of the die quickly attenuate the streams of extruded polymers to form extremely fine filaments. The filaments are then blown by high velocity air into a collecting screen, thus forming a self-bonded non-woven web. Alternatively, continuous filaments obtained by extrusion can be cut into pieces and then spread over a heated mandrel to form a non-woven web, followed by cooling.
    [0077] A non-woven web for use in composite materials can be produced by the non-woven fabrication process discussed above, without the need for any weaving technique. This web can take the form of a mat or weft made of randomly arranged continuous or cut fibers. The composition of the fibers includes a polymeric component and a conductive component, as in the case of the composite particles discussed above. As such, conductive polymer fibers have properties similar to composite particles. The nonwoven web is particularly suitable for interposing between them, and in contacting with respect to adjacent layers of dry structural reinforcing fibers (such as carbon fibers) in a dry fiber preform that is adapted for resin infusion. liquid, or as an interspersed between two adjacent prepeg layers during prepeg support.
    [0078] In resin infusion, a dry fiber preform (without resin) is injected with a curable liquid resin composition. When the nonwoven web consisting of conductive polymeric fibers is incorporated into said dry fiber preform, the polymeric component of conductive polymeric fibers in the web maintains the solid phase during resin infusion. Then, during the curing of the resin-infused fiber preform, the polymer component goes from phase transition to a fluid phase, upon dissolution in the resin.
    [0079] When the nonwoven web consisting of conductive polymeric fibers is used in pre-impregnation, the polymeric component of the conductive polymeric fibers in the web maintains its solid phase during prepeg support, then, during curing, is subjected the phase transition to a fluid phase, upon dissolution in the resin matrix of the pre-impregnated layers, as discussed above with reference to the interlaminar composite particles.
    [0080] In another embodiment, the conductive polymer fibers are part of a structural fiber preform adapted for resin infusion, wherein the structural preform is composed of reinforcing fibers combined with conductive polymer fibers. Furthermore, the structural preform can be molded into a three-dimensional configuration in accordance with the shape of the final composite structure to be fabricated. The fibers are combined in a way so as to provide a physical association of the fibers. Combining to provide a physical association can be by methods as known in the textile art, for example, sewing, knitting, pleating, punching, weaving, braiding, over-curling, knitting, seaming, aligning, twisting, winding, tying, spinning, positioning on the same fiber layer, positioned on different but adjacent fiber layers and the like. The conductive polymer fibers can be arranged between the aligned or misaligned reinforcing fibers, or in a stitched fashion, or as a multi-filament yarn composed of multiple conductive composite fibers and reinforcing fibers. Reinforcing fibers in this context are fibers made from carbon, glass, inorganic oxide, aramids, carbide, boron, ceramic, metal, metal-coated fibers or a combination thereof. The structural fiber preform is then injected with a liquid curable resin composition followed by curing to form a composite structure with conductive properties. The polymeric component of the conductive polymeric fibers undergoes the same liquid phase transition during cure as discussed above with reference to the composite particles.
    [0081] Also contemplated herein are non-pleated fabrics composed of a combination of reinforcing fibers and conductive polymer fibers. "Non-crimped" refers to a fabric, in which several layers of fibers are placed on top of each other and made into a fabric by stitching or applying a binder so that the fibers remain straight and without substantial crimping. Conductive polymer fibers can be present in one or more layers of the non-pleated fabrics. In addition, conductive polymer fibers can be non-uniformly present with respect to the reinforcing fibers to locally impart properties such as Z-direction conductivity and stiffening. Such non-pleated fabrics can be incorporated into a structural fiber preform adapted for resin infusion. applications
    [0082] The composite materials of the present invention find utility in any field where it is necessary to impart better conductivity to a composite material/structure. As an embodiment of the present disclosure, the z-direction conductivity of the composite materials of the present disclosure is at least an order of magnitude greater than measured values for conventional third generation carbon fiber reinforcement materials.
    [0083] The composite materials of this disclosure are applicable to the fabrication of components for transportation applications (e.g., aerospace, aeronautics, nautical and land vehicles), and including, for example, primary and secondary aircraft structures (fuselage, wings, bulkheads, etc.), space and ballistic structures. The composite materials of the present disclosure also find use in construction applications. Furthermore, the composite materials, in particular prepegs and prepeg supports of the present disclosure are particularly suitable for the fabrication of load bearing structures or impact resistant structures. EXAMPLES
    [0084] The examples that follow serve to illustrate some preferred embodiments of the present description, and test results thereof, but should not be construed as limiting the scope of the present disclosure in any way. Measurement Methods
    [0085] In the following examples, the following measurement methods were used:
    [0086] DC electrical conductivity in the Z direction
    [0087] The electrical conductivity of the cured composite materials was measured using a Burster-Resistomat 2316 milliohmmeter that records resistance values as the relationship between the applied voltage and current in a bridge method. Kelvin test probes were used to create contact between two sample surfaces. All measurements were performed in accordance with the 4-wire ambient temperature (RT) measurement method under normal humidity conditions.
    [0088] Measurements were performed on coupons extracted from defect-free panels, prepared according to the EN 2565 B method. Quasi-isotropic square samples of about 2 mm thick (side length = 40 mm ± 0, 1 mm) were characterized.
    [0089] Composite sample surfaces were prepared by removing the upper resin-rich layer to expose the carbon fibers underneath ensuring direct contact with the electrode. Next, a commercial silver paste was used to create two electrodes on opposing coupon surfaces. At least 5 samples per material and support were tested.
    [0090] DC electrical conductivity was calculated in [S/m] according to the following equation:
    where: R is the measured resistance [Ohm]; I is the thickness of the sample [m]; S is the surface area of the sample [m2] Particle Size Distribution
    [0091] Particle size distribution was measured using a Malvern Mastersizer 2000 operating in the range of 0.02 µm to 2000 µm. Example 1 Preparation of nickel-based conductive composite particles
    [0092] A sufficient amount of filament nickel (Ni) flakes (nickel powder 525 available from Novamet) to achieve a final concentration of 70% by weight was dispersed in a functionalized polymer polyethersulfone (PES) through a melt-mix process in a twin-screw extruder (Sumikaexel 5003P from Sumitomo). A pure sample of the same PSA polymer was used as a control. High shear screw profiles were used to optimize dispersion levels. The profiles include conventional mixing segments associated with chaotic mixing units in order to create the best balance between shear forces and pressure in the extruder barrel. The temperature conditions and profile of the process used are shown in Table 1. Table 1. Dispersion conditions of nickel/PES blend composite


    [0093] The resulting Ni/PES mixture was subjected to cryogenic milling to produce microscopic particles (i.e., "microparticles") having an average particle size of less than 60 µm using an Alpine cryogenic milling system equipped with means of different rotation grinding. Specifically, several steps using clove beater, swing beater and plate beaters were required to obtain the target particle size distribution. Fig. 4 shows an SEM image of micron-sized Ni/PES composite particles produced as the result of cryogenic milling. Example 2 Effect of nickel-based conductive microparticles on the electrical performance of composite structures
    [0094] The nickel/PES composite microparticles of Example 1 were dispersed through a spray process onto the surface of a unidirectional CYCOM®977-2-34%-194-IMS24K unidirectional carbon fiber tape (matrix impregnated) epoxy based) supplied by Cytec Engineered Materials Ltd, UK. Particle loading was 10% by volume based on the total volume of resin on the tape. A plurality of such tapes have been defined above, one on top of the other, with the microparticles positioned between adjacent tapes so as to form a quasi-isotropic 1.5mm thick test panel. The panel was then cured according to a 2 hour cure cycle at 180°C in an autoclave. This test panel was labeled “2A”.
    [0095] During the curing process, the particles were positioned in the resin-rich region between the adjacent carbon fiber layers, which defines the interlaminar region. The thermoplastic component of the composite microparticles dissolved in the epoxy-based matrix of the tapes during the curing cycle, releasing the metal component (as the conductive particles) into the interlaminar regions of the multilayer panel. In such a way, conductive structures or bridges located between adjacent carbon fiber layers were created.
    [0096] For comparison purposes, a similar test panel, labeled "Reference 1", was produced by the same method, but the microparticles of the PES/nickel composite were replaced with non-conductive, crosslinked thermoplastic (TP) particles. The z-direction conductivity values for the two test panels are shown in Table 2. Table 2. Intercalated composite particles and corresponding z-direction conductivity values

    [0097] Controlled introduction of Ni/PES composite microparticles into interlaminar regions of the 2A panel has been determined to produce more than an order of magnitude improvement in conductivity in the z-direction compared to the Reference 1 panel. It is believed that the reduction in the volume resistivity of the composite is the result of the increase in the number of electrical bridges created through the controlled dissolution mechanism of Ni/PES composite microparticles. Example 3 Effect of conductive interlaminar particles loading on the mechanical performance of composite structures
    [0098] Two different charges (10% and 20% by volume) of the same Ni/PES microparticles of composites used in Example 2 were dispersed separately on the surface of CYCOM®977-2-34%-194-IMS24K unidirectional tape of Cytec Engineered Materials, UK. Two test panels with different particle loads were formed by accumulating the strips with microparticles dispersed in them. The resulting test panels were evaluated to determine the effect of composite microparticles on thermomechanical properties. The test panel containing 10% microparticles was labeled "3B", and the test panel containing 20% microparticles was labeled "3C". For comparison purposes, a similar test panel, which does not contain Ni/PES microparticles from composites, was fabricated and labeled “REFERENCE 2”.
    [0099] The mechanical performance of the test panels is shown in Table 3. Table 3. Interleaved composite particle and corresponding mechanical performance

    [00100] The introduction of 10% and 20% by volume of the Ni/PES particles from composites into the 3B and 3C panels, respectively, was determined to produce 60% and 73% improvement, respectively, in resistance to delamination growth in Mode I compared to the REFERENCE panel 2. A simultaneous 10%-15% increase in resistance to delamination growth was also observed at Mode II values. In addition, the introduction of 10% Ni/PES composite microparticles resulted in a 25% increase in compressive strength after a 30J impact, significantly reducing the damaged area. Example 4. Effect of conductive silver-based microparticles on the electrical performance of composite structures
    [00101] A sufficient amount of CAP9 silver (Ag) powder (from Johnson Matthey, UK) was dispersed in commercially available polyethersulfone functionalized polymer one (SUMIKAEXEL 5003P from Sumitomo) through a melt blending process in an extruder of double thread, to reach a final concentration of Ag 70% by weight of the composite mixture (polymeric component + element component). High shear thread profiles were used. The temperature conditions and process profile used are shown in Table 1.
    [00102] The pellets produced from the extruder were further crushed in a cryogenic milling device to produce Ag/PES composite microparticles with an average particle size of less than 60 µm.
    [00103] The composite microparticles were dusted onto the surface of the unidirectional CYCOM®977-2-34%-194-IMS5131-24K tape as described in Example 2, and a plurality of resulting tapes were placed to form a panel quasi-isotropic. The panel was then cured at 180°C for 3 hours in an autoclave. A 10% by volume particle loading, based on the total resin content in which the panel was selected for this example. The resulting panel was labeled “4A”.
    [00104] The z-direction conductivity of the 4A panel was measured according to the method described above. Table 4 shows the comparison of conductivity in the z direction between panel 4A and the Reference panel 1 described in Example 2. Table 4. Intercalated particle composites and corresponding electrical performance

    [00105] The introduction of microparticles from Ag/PES composites has been shown to produce more than half an order of magnitude improvement in conductivity in the z direction, compared to the reference panel 1. Example 5 Effect of polymeric component of conductive composite microparticles on electrical performance of composite structures
    [00106] A conductive alternative "5A" composite blend was produced by dispersing a commercially available copper (Cu) granulate (CH-L7 from GGP Metalpowder AG) in a commercially available polyethersulfone (PES) functionalized polymer (SUMIKAEXEL 5003P from Sumitomo, UK) in a twin screw extruder as described in Example 1. A copper concentration of 65% by weight based on the total weight of the composite mixture was obtained.
    [00107] For comparison purposes, a “5B” conductive composite blend was produced by combining an identical content (65% by weight) of the same copper material in a commercially available polyamide (VESTOSINT 2159, available from Evonik, UK) , using the twin screw extruder described in Example 1. Process conditions are shown in Table 5. Table 5. Dispersion conditions for PES/copper composite and polyamide/copper blends

    [00108] In both cases, the pellets produced from the extruder were ground in a cryogenic grinding device to produce composite microparticles with an average (d50) size of less than 50 µm. The microparticles were then dispersed onto the surface of a unidirectional 977-2-34%-194-IMS24K tape to a 10 vol% particle load, based on the total resin content in the tape, before plating. A plurality of such tapes were placed in an intercalated stacking sequence to form the panels, as described in Example 2. The panels were then cured in an autoclave for 3 hours at 180°C.
    [00109] Conductivity values in the Z direction were recorded as described above and the results are shown in Table 6. The panel “Reference 1”, as revealed in Example 2 is used here for comparison. Table 6. Intercalated particle composites and corresponding performance


    [00110] Fig. 5A shows a cross section of the cured panel (5B) containing particles of Cu/polyamide composites in the interlaminar region and fig. 5B is an exploded view (in dark field) of a portion of the interlaminar region. It can be seen from FIGS. 5A and 5B that polyamide-based particles do not efficiently dissolve within the epoxy matrix during the cure cycle, thus limiting the formation of electrical bridges between layers of carbon fibers. Therefore, the introduction of the composite particles into the interlaminar region of the laminated panel did not result in any significant improvement in conductivity in the z-direction across the standard non-conductive thermoplastic interleaved panel (Reference 1).
    [00111] In contrast, the PES-based particles in panel 5A substantially dissolved in the epoxy matrix during the curing cycle, releasing the copper particles in the interlaminar composite panel regions. In such a form, conductive structures or bridges are created between adjacent carbon fiber layers. Fig. 6 shows a cross-sectional view of cured panel 5A containing 10% by volume Cu/PES composite particles. As a result of the controlled dissolution mechanism, Cu/PES composite particles have been shown to provide about an order of magnitude improvement in conductivity in the z-direction compared to non-conductive thermoplastic particles.
    [00112] The above results further demonstrate that the selection of suitable polymeric components for the composite particles is critical to realizing the dissolution mechanism described above, which, in turn, provides the improvements in the z-direction of conductivity for composite structures. Example 6.
    [00113] Effect of conductive particles: non-conductive particles in relation to electrical performance of composites
    [00114] Four different panels (7A-7D) were fabricated and cured as described in Example 2, using the Cu/PES composite particles described in Example 5 and the non-conductive thermoplastic (TP) particles of different conductive particles: proportions of non-conductive particles shown in Table 7. The z-direction conductivity of the cured panels was measured and the results are shown in Table 7. The "reference 1" panel, as disclosed in Example 2, is used here for comparison. Table 7. Effect of different proportions of conductive:non-conductive interlaminar particles on electrical performance of the composite

    [00115] As shown in Table 7, there is a clear trend in the improvement of conductivity in the z direction with increasing charge of the Cu/PES composite particles.
    [00116] Ranges described here are inclusive and independently combinable (for example, ranges from "up to about 25% by volume, or more specifically, about 5% by volume to about 20% by volume" is inclusive of all endpoints and the intermediate values of the ranges).
    [00117] Although various embodiments are described herein, it will be appreciated from the written description that various combinations of elements, variations or improvements thereto may be performed by those skilled in the art, and are within the scope of the present disclosure. Furthermore, many modifications can be made to adapt a given situation or material to the teachings of the present disclosure without departing from the essential scope of the present disclosure. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but that the invention include all embodiments that are within the scope of the appended claims.
    权利要求:
    Claims (16)
    [0001]
    1. Curable composite material, characterized in that it comprises: i) at least one structural layer (23, 24, 25) of reinforcing fibers impregnated with a curable resin matrix; and ii) at least one electrically conductive composite particle (20) adjacent or in proximity to said reinforcing fibers, said conductive composite particle comprising a conductive component and a polymeric component, wherein the polymeric component of the conductive composite particle comprises a or more polymers that are initially in a solid phase and substantially insoluble in the curable resin matrix prior to curing the composite material, but are capable of at least a partial phase transition to a fluid phase upon dissolution in the resin matrix during the curing cycle of the composite material.
    [0002]
    2. Composite material according to claim 1, characterized in that said curable resin matrix is a thermosetting composition, in which at least 50% of the polymeric component of the conductive composite particle is soluble in the resin matrix during the curing of the composite material, and in which the transition phase to the fluid phase occurs by dissolving the polymer component in the resin matrix.
    [0003]
    3. Composite material according to claim 1 or 2, characterized in that the conductive component of each electrically conductive composite particle (20) comprises one or more conductive materials having an electrical conductivity greater than 1 x 103S/m.
    [0004]
    4. Composite material according to any one of claims 1 to 3, characterized in that a) the conductive component of each electrically conductive composite particle (20) comprises one or more conductive materials selected from metallic materials, non-metallic conductive materials and their combinations; or b) the conductive component of the electrically conductive composite particle (20) comprises one or more metallic materials selected from silver, gold, platinum, palladium, nickel, copper, lead, tin, aluminum, titanium, alloys and their mixtures or c) the conductive component of the electrically conductive composite particle (20) comprises one or more non-metallic conductive materials selected from carbon, graphene, graphite and combinations thereof.
    [0005]
    5. Composite material according to any one of claims 1 to 4, characterized in that the polymeric component of the conductive composite particle comprises at least one thermoplastic polymer selected from the group consisting of: polyurethane, polyketone, polyamide, polyphthalamide, polystyrene, polybutadiene, polyacrylate, polyacrylic, polymethacrylate, polyethersulfone (PES), polyetherethersulfone (PEES), polyphenylsulfone, polysulfone, polyester, liquid crystal polymers, polyimide, polyetherimide (PEI), polyetherketone (PEKK), polyetheretherketone (PEEK), polyurethane , polyarylether, polyarylsulfide, polyphenylene, polyphenylene oxide (PPO), polyethylene oxide (PEO), polypropylene oxide, copolymers and combinations thereof.
    [0006]
    6. Composite material according to any one of claims 1 to 5, characterized in that the polymeric component of the conductive composite particle further comprises at least one thermosetting resin and a curing agent or a catalyst.
    [0007]
    7. Composite material according to any one of claims 1 to 6, characterized in that a plurality of electrically conductive composite particles (20) is present in a content of 0.1% to 25% by volume based on the volume of the total resin content in the composite material.
    [0008]
    8. Composite material according to any one of claims 1 to 7, characterized in that a plurality of electrically conductive composite particles (20) is present, and the particles have an average particle size of less than 150 µm, or within the range of 10 µm to 60 µm.
    [0009]
    9. Composite material according to any one of claims 1 to 8, characterized in that it further comprises non-conductive particles, in which the composite particles combined with non-conductive particles are present in a content of up to 25% by volume with based on the volume of the total resin content in the composite material.
    [0010]
    10. Composite material according to any one of claims 1 to 9, characterized in that said curable resin matrix comprises one or more thermosetting resins selected from the group consisting of: epoxy resins, bismaleimide, vinyl ester resins, cyanate ester resins, isocyanate modified epoxy resins, phenolic resins, benzoxazine, formaldehyde condensed resins, polyesters, acrylics, and combinations thereof; and/or further comprises a second fiber reinforcing structural layer impregnated with a curable resin matrix, wherein said at least one conductive composite particle is located between the fiber reinforcing layers of the first and second structural layers.
    [0011]
    11. A method for fabricating a composite structure, characterized in that it comprises: (a) dispersing at least one conductive material in a polymeric material to form a composite blend; (b) optionally treating said mixture by heating; (c) forming micron-sized conductive composite particles from the composite mixture, said particles having an average particle size of less than 150 µm; (d) optionally thermally treating the micron-sized conductive composite particles; and forming a composite material as defined in claim 1, comprising at least one layer of reinforcing fibers impregnated with a curable resin matrix, and a plurality of micron-sized conductive composite particles adjacent to the reinforcing fibers, wherein the material polymer in each conductive composite particle comprises one or more polymers that are initially in a solid phase and substantially insoluble in the curable resin matrix prior to curing of the resin matrix, but is capable of at least passing from the partial transition phase to a phase of fluid by dissolving the resin matrix during the curing cycle of the composite materials; and optionally further comprises: (e) curing the composite material, wherein the polymeric material in the conductive composite particles passes at least from the partial transition phase to a fluid phase, by dissolving in the resin matrix during curing, and after When curing, the conductive component of the conductive composite particles acts as conductive bridges between adjacent layers of reinforcing fibers.
    [0012]
    12. Method according to claim 11, characterized in that said curable resin matrix is a thermosetting composition, in which 50% to 100% of the polymeric component of each conductive composite particle are soluble during curing.
    [0013]
    13. Method according to claim 11, characterized in that step (a) is performed in an extruder and the extruded composite mixture is in the form of pellets.
    [0014]
    14. Method according to any one of claims 11 to 13, characterized in that the conductive material to be dispersed in phase (a) is in a form selected from the group consisting of flakes, powders, dendrites, fibers , spheres, metal-coated products, and combinations thereof; or (b) the conductive component of the electrically conductive composite particle (20) comprises one or more metallic materials selected from silver, gold, platinum, palladium, nickel, copper, lead, tin, aluminum, titanium, alloys and mixtures thereof; or (c) the conductive material is selected from the group consisting of: cut carbon fibers, graphite flakes, graphite nanoplates, carbon black, single-walled carbon nanotubes (SWCNT), double-walled carbon nanotubes ( DWCNT), multi-walled carbon nanotubes (MWCNT), carbon nanofibers, carbon nanospheres, carbon nanorods, fullrenes, carbon nanocords, carbon nanoribbons, carbon nanofibers, carbon nanoneedles, carbon nanosheets, graphenes , carbon nanocones, carbon nanorollers with roll-like shapes, boron nitride based products, with or without conductive coating.
    [0015]
    15. Method according to any one of claims 11 to 14, characterized in that the composite material is formed by impregnating the layer of reinforcing fibers with the curable resin matrix, and the conductive composite particles are incorporated in the matrix of curable resin prior to resin impregnation, and wherein the conductive composite particles remain on the outer surfaces of the reinforcing fiber layer after impregnation.
    [0016]
    16. Method according to claim 11, characterized in that the composite material is formed by: placing two layers of curable resin matrix without conductive composite particles in contact with a surface of a layer of reinforcing fibers, followed by applying heat and pressure to cause the resin matrix to impregnate the reinforcing fibers; and subsequently, placing a layer of matrix resin containing the conductive composite particles in contact with a surface of the layer impregnated with reinforcing fibers.
    类似技术:
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    BR112014025708B1|2021-07-20|CURABLE COMPOSITE MATERIAL, CURABLE COMPOSITE LAMINATE, AND METHOD FOR MANUFACTURING A COMPOSITE STRUCTURE
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    AU2014384605B2|2017-09-14|Composite materials with electrically conductive and delamination resistant properties
    同族专利:
    公开号 | 公开日
    TW201343735A|2013-11-01|
    AU2017204658B2|2018-11-08|
    US20180029686A1|2018-02-01|
    EP2838702B1|2020-06-10|
    GB201206885D0|2012-06-06|
    ES2813531T3|2021-03-24|
    US20160107739A1|2016-04-21|
    JP6259446B2|2018-01-10|
    AU2013289104A1|2014-10-02|
    TWI567118B|2017-01-21|
    CA2870921C|2021-05-18|
    KR20150003800A|2015-01-09|
    US10507900B2|2019-12-17|
    JP2015518436A|2015-07-02|
    KR20200101468A|2020-08-27|
    US10370079B2|2019-08-06|
    JP2018039273A|2018-03-15|
    WO2014011293A3|2014-03-20|
    RU2014146307A|2016-06-10|
    KR102251006B1|2021-05-13|
    WO2014011293A2|2014-01-16|
    CA2870921A1|2014-01-16|
    EP2838702A2|2015-02-25|
    RU2631299C2|2017-09-20|
    MX2014012265A|2015-03-09|
    CN104334327B|2016-10-12|
    KR102146500B1|2020-08-21|
    AU2017204658A1|2017-07-27|
    AU2013289104B2|2017-07-06|
    JP6568922B2|2019-08-28|
    MY169057A|2019-02-12|
    CN104334327A|2015-02-04|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US4234648A|1979-01-29|1980-11-18|Hexcel Corporation|Electrically conductive prepreg materials|
    US5009927A|1988-11-29|1991-04-23|Hexcel Corporation|Method for coating fabric surface with electrically conductive film|
    JPH0741577Y2|1989-04-28|1995-09-27|スズキ株式会社|Welding cable connection structure of spot welding robot|
    US4957801A|1989-05-17|1990-09-18|American Cyanamid Company|Advance composites with thermoplastic particles at the interface between layers|
    EP0561064A1|1992-03-20|1993-09-22|Lantor B.V.|Conducting reinforced plastics|
    JP3312441B2|1993-07-30|2002-08-05|東レ株式会社|Prepreg and fiber reinforced plastic|
    JP3463898B2|1995-02-06|2003-11-05|新日本石油株式会社|Heating element and network structure for heating element|
    US7037865B1|2000-08-08|2006-05-02|Moldite, Inc.|Composite materials|
    US20050271838A1|2001-02-15|2005-12-08|Integral Technologies, Inc.|Low cost vehicle fuel system components manufactured from conductive loaded resin-based materials|
    CN100341916C|2002-11-28|2007-10-10|三菱丽阳株式会社|Epoxy resin for prepreg, prepreg, fiber-reinforced composite material, and processes for producing these|
    DE102004025378B4|2004-05-24|2011-01-13|Airbus Operations Gmbh|Window frame for aircraft|
    JP4969363B2|2006-08-07|2012-07-04|東レ株式会社|Prepreg and carbon fiber reinforced composites|
    CN101500774B|2006-09-29|2013-10-30|东丽株式会社|Forming-molding tool and process for producing preforms and fiber reinforced plastics with tool|
    EP2540755B1|2007-04-17|2014-09-24|Hexcel Corporation|Composite material with blend of thermoplastic particles|
    GB0622060D0|2006-11-06|2006-12-13|Hexcel Composites Ltd|Improved composite materials|
    JP5359125B2|2007-08-29|2013-12-04|東レ株式会社|Prepreg and carbon fiber reinforced composites|
    US7935214B2|2007-11-06|2011-05-03|The Boeing Company|Toughened resin fiber laminates with titanium particles|
    GB0805640D0|2008-03-28|2008-04-30|Hexcel Composites Ltd|Improved composite materials|
    GB2464085A|2008-06-07|2010-04-07|Hexcel Composites Ltd|Improved Conductivity of Resin Materials and Composite Materials|
    DE102008038294B4|2008-08-18|2013-07-18|Airbus Sas|Process for producing a fiber composite component and semi-finished textile therefor|
    AU2010213946B2|2009-02-16|2012-09-06|Cytec Technology Corp.|Conductive surfacing films for lightning strike and electromagnetic interference shielding of thermoset composite materials|
    CN102905888B|2009-12-18|2016-03-09|塞特克技术公司|Give the method for material conductivity used in composite article manufacture and material thereof|
    FR2954356B1|2009-12-22|2012-01-13|Hexcel Reinforcements|NEW INTERMEDIATE MATERIALS PRODUCED BY INTERCONNECTION WITH INTERLAYING OF SAILED YARNS|
    JP2011144213A|2010-01-12|2011-07-28|Toray Ind Inc|Epoxy resin composition for carbon fiber-reinforced composite material, prepreg and carbon fiber-reinforced composite material|
    GB201008884D0|2010-05-27|2010-07-14|Hexcel Composites Ltd|Improvements in composite materials|
    JP2013215124A|2012-04-06|2013-10-24|Sumio Yamamoto|Breaking tine with protrusion for tiller|WO2014139031A1|2013-03-15|2014-09-18|Concordia University|Methods for fabricating morphologically transformed nano-structuresand tunable nanocomposite polymer materials, and devices using such materials|
    GB201308021D0|2013-05-03|2013-06-12|Rolls Royce Plc|Composite structure|
    JP6118655B2|2013-06-21|2017-04-19|東邦テナックス株式会社|Prepreg, method for producing the same, and fiber-reinforced composite material using the same|
    GB201322093D0|2013-12-13|2014-01-29|Cytec Ind Inc|Compositive materials with electrically conductive and delamination resistant properties|
    EP3122637B1|2014-03-25|2018-10-10|Zodiac Aerosafety Systems|Aviation fuel tank with rigid wall for crash energy absorption|
    WO2016003339A1|2014-07-03|2016-01-07|Saab Ab|A composite article having multifunctional properties and method for its manufacture|
    FR3023746B1|2014-07-21|2016-07-29|Univ Paul Sabatier - Toulouse Iii|PROCESS FOR PREPARING AN ELECTRICALLY CONDUCTIVE LAMINATED COMPOSITE STRUCTURE|
    US10544274B2|2014-07-28|2020-01-28|Toho Tenax Co., Ltd.|Prepreg and fiber-reinforced composite material|
    EP2979981B1|2014-08-01|2017-01-25|Airbus Defence and Space GmbH|Lightning protection layer for fibre composite structures|
    US9845142B2|2014-08-15|2017-12-19|The Boeing Company|Conductive thermoplastic ground plane for use in an aircraft|
    EP3197674B1|2014-09-22|2021-11-10|Cytec Industries Inc.|Composite materials with high z-direction electrical conductivity|
    US20160304210A1|2014-10-15|2016-10-20|Rosemount Aerospace Inc.|One-piece air data probe|
    FR3028205B1|2014-11-10|2018-01-05|Airbus Operations|METHOD FOR MANUFACTURING A PANEL OF COMPOSITE MATERIAL INCORPORATING LIGHTNING PROTECTION AND PANEL OF COMPOSITE MATERIAL MANUFACTURED ACCORDING TO SAID METHOD|
    EP3255083B1|2015-02-05|2021-09-15|Toray Industries, Inc.|Preform, fiber-reinforced composite material, and method for manufacturing fiber-reinforced composite material|
    US20160302334A1|2015-04-10|2016-10-13|Tyco Electronics Corporation|Cable Shielding Assembly and Process of Producing Cable Shielding Assembly|
    GB201508375D0|2015-05-15|2015-07-01|Airbus Operations Ltd|Method of forming composite structures|
    TWI567757B|2015-06-03|2017-01-21|財團法人紡織產業綜合研究所|Electrically conductive composition|
    CN105185597B|2015-08-13|2018-01-05|深圳市来源新材料科技有限公司|A kind of graphene metal composite electrode material for super capacitor and preparation method thereof|
    US10550291B2|2015-08-25|2020-02-04|Hitachi Chemical Co., Ltd.|Core-shell, oxidation-resistant, electrically conducting particles for low temperature conductive applications|
    TWI589525B|2015-09-02|2017-07-01|奈創國際控股有限公司|Graphene sheet combining graphite flake structure and its manufacturing method, and slurry for manufacturing the same|
    JP6704229B2|2015-09-14|2020-06-03|リンテック オブ アメリカ インコーポレーテッドＬｉｎｔｅｃ ｏｆ Ａｍｅｒｉｃａ， Ｉｎｃ．|Flexible sheet, heat conductive member, conductive member, antistatic member, heating element, electromagnetic wave shield, and method for manufacturing flexible sheet|
    EP3374165A1|2015-11-12|2018-09-19|Cytec Industries Inc.|Hybrid veil as interlayer in composite materials|
    US20170232133A1|2016-02-16|2017-08-17|Tamicare Ltd.|Articles and Method for Improved Transfer of Bodily Fluids|
    RU167990U1|2016-03-18|2017-01-16|Александр Евгеньевич Сулим|Construction material|
    WO2017180784A1|2016-04-12|2017-10-19|Trillium Marketing Inc.|Bi-polymer thermoplastic|
    WO2017179666A1|2016-04-13|2017-10-19|東邦テナックス株式会社|Prepreg, fiber-reinforced composite material and surface-modified reinforcing fibers|
    US10106661B2|2016-06-22|2018-10-23|Hexcel Corporation|Composite material with thermoplastic toughened novolac-based epoxy resin matrix|
    US10208176B2|2016-06-22|2019-02-19|Hexcel Corporation|Composite material with thermoplastic toughened novolac-based epoxy resin matrix|
    US10472474B2|2016-06-22|2019-11-12|Hexcel Corporation|Semipreg with thermoplastic toughened novolac-based epoxy resin matrix|
    GB2552170B|2016-07-11|2022-01-12|Lentus Composites Ltd|Fuel pipe|
    US9868835B1|2016-08-11|2018-01-16|Ford Global Technologies, Llc|Bio-based polyurethane foam materials including graphite materials|
    DE102016217735A1|2016-09-16|2018-03-22|Carl Zeiss Smt Gmbh|Component for a mirror assembly for EUV lithography|
    EP3299297B1|2016-09-27|2018-12-12|AIRBUS HELICOPTERS DEUTSCHLAND GmbH|A rotary wing aircraft with a structural arrangement that comprises an electrically conductive connection|
    CN108084655B|2016-11-21|2021-06-22|航天特种材料及工艺技术研究所|Low-temperature-resistant epoxy resin material and preparation method thereof|
    CN108146609A|2016-12-02|2018-06-12|中国航空工业集团公司成都飞机设计研究所|A kind of composite aircraft structure with transmission of electricity|
    CN110089208B|2016-12-13|2021-02-26|阿莫绿色技术有限公司|Flexible electromagnetic wave shielding material, electromagnetic wave shielding circuit module, and electronic device|
    EP3554786A1|2016-12-15|2019-10-23|SABIC Global Technologies B.V.|Pellet comprising an axial core and a polymer sheath, and its manufacture|
    EP3568432A1|2017-01-11|2019-11-20|SABIC Global Technologies B.V.|Composition with thermal conductivity and laser plating performance by core-shell structure lds additive with metal compounds coated on mineral filler surface|
    EP3689498A4|2017-09-27|2021-03-24|DOWA Electronics Materials Co., Ltd.|Silver powder mixture, method for producing same, and conductive paste|
    CN108063016B|2017-12-26|2019-12-03|浙江豆豆宝中药研究有限公司|A kind of integrated circuit conductive adhesive film composite conducting particles and preparation method thereof|
    EP3564018A1|2018-05-04|2019-11-06|Siemens Gamesa Renewable Energy A/S|Manufacturing method and tool for carbon parts|
    JP6922946B2|2018-07-20|2021-08-18|株式会社デンソー|Resin member and manufacturing method of resin member|
    US11136480B2|2018-08-01|2021-10-05|The Boeing Company|Thermal spray plastic coating for edge sealing and fillet sealing|
    JP2020055912A|2018-09-28|2020-04-09|京セラ株式会社|Resin composition for electrode formation, and chip type electronic component and method for manufacturing the same|
    FR3097160A1|2019-06-14|2020-12-18|Liebherr-Aerospace Toulouse Sas|MANUFACTURING PROCESS OF AN ELECTRICALLY CONDUCTIVE THERMOPLASTIC COMPOSITE MATERIAL|
    CN110713611A|2019-07-25|2020-01-21|北京汽车集团有限公司|Interlaminar modification method of fiber reinforced composite material and fiber reinforced composite material|
    US20210031942A1|2019-07-30|2021-02-04|The Boeing Company|Lightning strike protection|
    TWI718819B|2019-12-19|2021-02-11|財團法人工業技術研究院|Conductive fiber and method for fabricating the same|
    CN111223612A|2020-01-13|2020-06-02|杭州慈源科技有限公司|Normal temperature superconducting wire|
    CN111403080A|2020-03-24|2020-07-10|东莞讯滔电子有限公司|Cable and manufacturing method thereof|
    WO2021222990A1|2020-05-08|2021-11-11|Titomic Limited|A composite structure|
    CN114075344A|2020-08-19|2022-02-22|华为机器有限公司|Composite base material, electronic device, and method for manufacturing composite base material|
    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-10-29| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-12-08| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2021-06-08| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-07-20| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 15/04/2013, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    GBGB1206885.4A|GB201206885D0|2012-04-19|2012-04-19|Composite materials|
    GB1206885.4|2012-04-19|
    PCT/US2013/036555|WO2014011293A2|2012-04-19|2013-04-15|Composite materials|
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