 method for protecting a substrate against lightning
专利摘要:
Method for protecting a substrate against lightning The invention relates to a method for protecting a substrate against lightning including providing a lightning protective composition to the substrate. the lightning protection composition comprises a reactive organic compound and a conductive charge which, during the curing of the organic compound, is capable of self-assembly in a heterogeneous structure comprised of a three-dimensional, continuous, metal network located between polymer-rich domains (continuous or semicontinuous). the resulting composition has exceptionally high thermal and electrical conductivities. 公开号:BR112012000203B1 申请号:R112012000203 申请日:2010-06-11 公开日:2020-01-28 发明作者:d huffman Nicholas；b carruthers Seth 申请人:Lord Corp； IPC主号:
专利说明:
METHOD FOR PROTECTING A SUBSTRATE AGAINST LIGHTNING FIELD OF THE INVENTION [0001] The present invention relates to electrically conductive polymeric materials. More particularly, the present invention relates to electrically conductive compositions used for lightning protection (LSP) (Lightning Strike Protection). BACKGROUND OF THE INVENTION [0002] Due to excellent combinations of strength and weight, composite materials are increasingly being used to replace aluminum in aircraft structures. Although this provides significantly increased fuel efficiency and / or increased load capacity, aircraft structures unfortunately become more vulnerable to lightning damage. This increased vulnerability stems from the lower electrical conductivity of composites, such as those based on carbon fiber reinforced materials, compared to those of aluminum metal. Naturally, the less conductive a material is, the more energy it will absorb due to resistive heating mechanisms. It has been reported that carbon fiber composites can absorb nearly 2,000 times the amount of energy from lightning compared to the same mass of aluminum. The increased absorbed energy leads to increased direct and indirect effects. [0003] Direct effects are associated with physical or direct damage to structures carrying a load, with the worst types of damage being severe punctures through composite laminates. Indirect effects are associated with electrical storms caused by the massive electromagnetic field of lightning. These storms can disrupt aircraft control and in turn compromise the pilot's ability to control the aircraft. Indirect effects have lately been Petition 870190126679, of 12/02/2019, p. 10/58 2/45 more worrying since aircraft controls are increasingly shifting to fly-by-wire control systems. It is for this reason that massive amounts of electromagnetic interference (EMI) protection materials (Electromagnetic Interference) in the form of boxes, gaskets, metal sheets and meshes, adhesives, metal shielding, etc., are used to protect electrical components, wiring and connections. [0004] In order to protect composites from the effects mentioned above, aircraft designers seek to maintain strong electrical currents on the aircraft's external surface by integrating highly conductive external parts into the composite structure. Several attempts to produce such external lightning protection (LSP) parts have been made and / or proposed, each with varying degrees of success. For example, metal wire meshes and expanded metal sheets (EMF) (Expanded Metal Foil) based on metals such as copper, aluminum or bronze have been embedded in surface (or adhesive) films and treated with base composite prepegs. Alternatively, individual strands were intertwined with carbon fibers to produce hybrid prepegs. Similarly, metal deposition techniques have been employed to coat carbon fibers or other reinforcement fibers in their raw or woven forms. In addition to metallized fibers, flame spraying is another LSP approach used, which involves deposition of molten metal, typical aluminum on substrates. [0005] More recent attempts have been made to overcome the lack of z conductivity in fiber prepegs as well as the meshes mentioned above, EMFs, hybrids and metallized fibers; this involved incorporating conductive charges of high aspect ratio such as carbon nanotubes (or nanofibers), graphene or nanofilaments to resins that are used as a stand-alone adhesive film or in conjunction with carbon fiber or carbon fiber prepeg. Similarly, low aspect ratio particles or their combinations Petition 870190126679, of 12/02/2019, p. 11/58 3/45 with high aspect ratio particles have been used for the same purpose. These approaches, while much more efficient at high conductivity over heavily loaded resins, do not yet have the conductivity and maximum current loading capacity required in LSP applications. Other approaches have attempted to alleviate this issue by replacing non-conductive resins with intrinsically conducting polymers. Unfortunately, these materials and those mentioned above still suffer from limited lightning protection, substantial weight gain, manufacturing challenges and / or limitations in basic properties such as thermal and electrical conductivities, current carrying capacity, viscosity (or handling) and / or mechanical properties. [0006] Of the different systems mentioned in the literature, those based on sheet metal, particularly EMFs, were the most successful in being reduced to practice. Despite their presence on most fixed and rotary wing aircraft, EMFs have several unwanted characteristics. For example, EMF systems exhibit limited indirect protection by providing protection over a limited frequency range. EMF systems have been shown to be very susceptible to frequencies in and above the 1 GHz band. Because of this, aircraft designers often add extra or more robust protective materials to the aircraft to protect against disruptions in electrical communications which in turn adds considerable weight. [0007] EMF systems also suffer from handling issues during manufacturing and repairs. Specifically, EMFs must be integrated with adhesive films at the supplier or Original Equipment Manufacturer (OEM), which can be challenging and expensive. In addition, EMFs are difficult to shape in contoured modeling, suffer from stickiness issues and are easily wrinkled and damaged during normal handling and cutting operations. There are also issues with maintaining Petition 870190126679, of 12/02/2019, p. 12/58 4/45 electrical integrity between panels during joining, joining and earthing operations. For such reasons, OEMs are forced to stretch these materials by hand, thereby leading to considerable labor time and cost. Several attempts have been made to automate the stretching of EMF with little success due to these same issues in addition to weight penalties due to the overlap of EMF in many joints. In addition to handling, metal meshes based on aluminum and copper are prone to corrosion due to differences in galvanic potentials between the metal and the base carbon. To combat this issue, insulation sheets are often added between the EMF layer and the carbon sheets. Unfortunately, adding a sheet adds extra steps, increases labor, costs and adds more weight to the aircraft. [0008] Repair is also an issue with EMF systems. Damaged sheets must be properly removed through sanding and cutting or chamfering operations and patched with new EMF material. Joining the new sheet to the existing sheet so that the conductive strokes line up again is a challenge as well as dealing with porosity effects that arise from air entrapment. [0009] Given the above, there is a need for improved LSP materials which are: highly conductive in the z direction, lighter in weight, corrosion resistant, less complex (ie less layers) and easy to apply and integrate during assembly and repair of composite structures and correspondingly capable of being automated in a manufacturing operation. SUMMARY OF THE INVENTION [0010] In a preferred embodiment of the present invention, the materials described in U.S. Patent Application No. 12 / 055,789 filed March 26, 2008 and published as commonly owned U.S. 2010/0001237, and Petition 870190126679, of 12/02/2019, p. 13/58 5/45 incorporated here as a reference in its entirety, are used as a conductive matrix formed in situ during curing and applied to a substrate to provide direct and indirect protection against lightning. [0011] In an effort to address the various issues with existing LSP systems, one embodiment of the present invention employs a lightning protective composition comprising a reactive organic compound and electrically conductive charge that is capable of self-assembly during curing of the organic compound. a heterogeneous structure comprised of a three-dimensional, continuous, metal network located between polymer-rich domains (continuous or semi-continuous) whose electrical conductivity is within several orders of magnitude than that of mass metals. [0012] In another embodiment of the present invention, a method for protecting a substrate against lightning is provided comprising providing a substrate, providing a lightning protection composition to the substrate, where the lightning protector comprises a curable, charged, capable material. self-assembly to form conductive courses during a curing process. In another embodiment of the present invention, the curable material comprises a curable organic compound and a filler, preferably a coated silver filler, and the filler and the organic compound exhibit an interaction during the curing of the organic compound, said interaction causing the load carry out self-assembly on conductive strokes. [0013] In yet another embodiment of the present invention, the composition is cured in this way by forming conductive courses therein, and the conductivity of the cured self-assembled composition is greater than 100 times the conductivity of a non-self-assembled composition having an equivalent amount of conductive charge. [0014] In additional embodiments of the present invention, the compound Petition 870190126679, of 12/02/2019, p. 14/58 6/45 curable organic comprises diglycidyl bisphenol F ether and the curable organic compound further comprises a curing agent, preferably comprising a polyamine anhydride adduct based on the reaction between phthalic anhydride and diethylene triamine. [0015] In an additional embodiment of the present invention, the lightning protective composition further provides protection against electromagnetic radiation having a frequency between 1 MHz and 20 GHz, where said protection reduces electromagnetic radiation by at least 20 decibels. [0016] In another aspect of the present invention, a step of providing a lightning protection composition to a substrate comprises the following steps: identifying a damaged section of a lightning protection system comprising at least one discontinuous conductive course, deposition of the composition in the damaged section and curing of the deposited composition to provide at least one self-assembled conductive course completing the at least one discontinuous conductive course in the damaged section. [0017] In additional embodiments of the present invention, the damaged lightning protection system comprises at least one of a conductive expanded metal sheet, metal mesh, carbonometal fiber, metallized carbon or charged conductive polymer and in another embodiment the Damaged lightning protection system comprises a curable material capable of self-assembly to form conductive strokes during a curing process. [0018] In a further aspect of the present invention, a method for non-destructive testing of a lightning protective composite (LSP) is provided comprising providing an electrically conductive composition capable of providing lightning protection, measuring an electrical property of the composition and equation of electrical property measured from composition to Petition 870190126679, of 12/02/2019, p. 15/58 7/45 electrical conductivity of a previously degraded sample of the composition to determine the degree of degradation of the composite. In one embodiment of the present invention, the composition comprises a curable material capable of self-assembly to form conductive strokes during a curing process. And in another embodiment of the present invention, the electrical property comprises electrical resistivity. [0019] Due to the heterogeneous structure formed, the LSP composition is capable of inducing a percolated network of conductive particles in considerable particle concentrations below those of traditional compositions that have homogeneous structures comprised of particles uniformly located throughout the polymer matrix. In addition, the heterogeneous structure formed during curing allows the sintering of particles in this way eliminating the contact resistance between the particles and in turn leading to drastic improvements in thermal and electrical conductivities. In addition, the continuous course of sintered metal allows charging of substantial amounts of heat and electrical current encountered during a lightning event. The combination of lower load and related self-assembly of continuous strokes allows LSP materials that are lighter in weight and easier to manufacture and repair than are desirable for fuel savings, load capacity ratios and construction and repair ratios. [0020] Due to its isotropic nature, the composition is conductive in all orthogonal directions, thus leading to significantly improved electrical and thermal conductivities in the z direction of composite structures. In turn, this improvement allows for considerable reduction in capacity effects and heat formation associated with layers of non-conductive resins present in the composite laminate as well as existing and similar EMF LSP systems. Petition 870190126679, of 12/02/2019, p. 16/58 8/45 [0021] In another embodiment of the present invention, because of the ability of the organic component to react and form covalent bonds, it can be easily co-cured with or cured on reactive or non-reactive substrates (for example, thermoplastic or a thermoset previously) reacted), respectively. Furthermore, proper selection of resin chemistry potentially allows the replacement of one or more layers typically found on the outside of an aircraft, such as primer and coating layers used to paint the aircraft. Furthermore, with proper load selection, it is capable of providing performance against lightning and corrosion without the need for an insulation sheet. [0022] Also, because of its isotropic, highly conductive nature, it is capable of being used as a functional material for the purpose of lightning protection and, but not limited to, protection against electromagnetic fields, elimination of static charge formation and a heat conduit for melting ice (e.g., defrost material). In addition, the multifunctional ability of the composition solves the issues of having to combine metallic structures, for example, EMFs, with adhesive films before their integration into the composite structure. [0023] In addition, the uncured composition (stage A, stage B, but not stage C) has desirable handling properties and is easily adaptable to various forms of application. Such forms include, but are not limited to, an applicable adhesive, a spray coating, an adhesive film or a resin to be used in or in conjunction with a composite fiber tape or prepeg. [0024] In a further embodiment of the present invention, the self-assembly composition can be used to produce a laminated structure of two or more layers so that the top layer comprises the conductive self-assembly composition and the base layers comprise Petition 870190126679, of 12/02/2019, p. 17/58 9/45 layers of electrically conductive or non-conductive resin, lighter weight. In addition, the laminated structure provides increased surface conductivity while maintaining a given weight with respect to a monolithic film of lower surface conductivity. In addition, the thickness of each layer can be varied to further increase the conductivity of the surface while maintaining a given weight. [0025] Still, in an embodiment of the present invention, the uncured composition is employed in combination with an existing LSP system to create a unique hybrid structure in this way producing attractive combinations of protection against LSP and weight. Examples include, but are not limited to, the self-assembling material used as a stage B film for fitting solid metal sheets, EMFs, metallized fibers, metallized woven fibers, metallized nonwovens (for example, coverings) or fiber bundles of metalcarbon. [0026] In a further embodiment of the present invention, the self-assembled composition further provides secondary protection to a substrate. For example, although an initial lightning strike can create physical damage in the immediate area of the lightning strike, electrical current can arise through the substrate / structure and damage electrical components or distant surfaces. The self-assembling conductive material of the present invention provides a means for dissipating and controlling this electrical storm in addition to providing primary protection to the immediate area of lightning. [0027] In another embodiment of the present invention, the self-assembly composition is capable of electrically bridging interfaces associated with the assembly of different sections of LSP materials or during the repair of LSP materials. In additional embodiments of the present invention, the material is applied as an uncured spray coating, uncured (non-stage C) film adhesive or as a flexible cured film that is bonded using a Petition 870190126679, of 12/02/2019, p. 18/58 10/45 secondary adhesive or resin that is optionally loaded with a conductive charge. In a further embodiment of the present invention, the existing or bonding substrate to be repaired or bonded may be of the same composition as the heterogeneous self-assembling material or be based on existing LSP systems such as those based on, but not limited to, EMFs . [0028] Still, the self-assembly nature of the composition makes it possible to use automatic equipment for applying LSP to composite structures. Examples include, but are not restricted to, applying the self-assembling material in a spray form using automatic spray equipment so that the sprayed material is applied to the outside of the uncured fiber reinforced polymer in a male mold structure or to the surface of a female mold structure that has been pre-treated with a release agent. In addition, the self-assembling material could be applied in combination with multiple unidirectional filaments (for example, fiber or tape) using automatic tape or fiber laying machines. The ability to form continuous electrically conductive courses following curing of adjacent filaments overcomes the issues mentioned above associated with prior art materials. [0029] Also, due to its isotropic, highly conductive nature, the materials discussed here lend themselves to quantitative non-destructive testing. In a further embodiment of the present invention, the conductivity of the cured composition can be measured for the purposes of, but not limited to, evaluation of defects during manufacture of the protected part, evaluation of the degree of damage to the LSP material or degradation of the material of performance of materials in the field. [0030] In this way, instead of being widely described, the most important features of the invention in order that the detailed report that follows can be better understood and in order that the present contribution to the Petition 870190126679, of 12/02/2019, p. 19/58 11/45 technique can be better understood. There are, of course, additional features of the invention which will be described below and which will form the subject matter of the claims attached to it. In this regard, before explaining the various modalities of the invention in detail, it should be understood that the invention is not limited in its application to the details and construction and to the disposition of the components shown in the report that follows or illustrated in the drawings. The invention is capable of other modalities and of being practiced and carried out in several ways. [0031] It should also be understood that the phraseology and terminology here are for the purpose of description and should not be considered as limiting in any respect. Those skilled in the art will understand the concepts upon which the present invention is based and which can readily be used as the basis for designating other structures, methods and systems for carrying out the various purposes of the present development. It is important that the claims are considered to include such equivalent constructions, as long as they do not depart from the spirit and scope of the present invention. [0032] So that the characteristics, advantages and objects of the invention mentioned above, as well as others that will become more apparent, are obtained and can be understood in detail, a more particular description of the invention summarized briefly above may have been by reference to its modality that is illustrated in the attached drawings, drawings that form part of the report and where equal reference characters designate equal parts in all the various views. It should be noted, however, that the attached drawings illustrate only preferred and alternative modalities of the invention and should not, therefore, be considered to limit its scope, since the invention can admit additional equally effective modalities. Petition 870190126679, of 12/02/2019, p. 20/58 12/45 BRIEF DESCRIPTION OF THE DRAWINGS [0033] Figure 1 is a view of a composite laminate in an embodiment of the present invention. [0034] Figure 2 is a graph of effectiveness of electromagnetic protection versus frequency for a self-assembled material used in a modality of the present invention. [0035] Figure 3 is a graph of damage to an LSP composite in an embodiment of the present invention after a lightning strike in Zone 1A versus the electrical resistance of the coating surface. DETAILED DESCRIPTION OF THE INVENTION [0036] In a first embodiment of the present invention method for protecting a substrate against lightning is provided comprising providing a substrate and providing a lightning protection composition to the substrate, where the lightning protective composition comprises a curable material , loaded, capable of self-assembly to form conductive courses during a curing process. The conductive charge performs self-assembly in conductive strokes during curing of the polymer matrix to provide a conductive LSP material that addresses many of the disadvantages of prior art materials. [0037] The self-assembly and structure formation mechanism is obtained through the appropriate selection of component materials and adherence to particular processing conditions. In one embodiment of the present invention, the charge component comprises a conductive charge (thermal, electrical or both) and the organic compound comprises a monomer and optionally a curing agent. The formation of load-rich domains during reaction of the organic material allows charge-to-charge particle contacts to be made. In the presence of heat the particles can sinter more together. Petition 870190126679, of 12/02/2019, p. 21/58 13/45 Sintering eliminates contact resistance between previously uninterintered charge particles in this way, substantially improving the thermal and / or electrical conductivity of the composite. [0038] Although not completely understood and not wishing to be limited by this theory, self-assembly and domain formation and sintering are believed to be sensitive to the curing temperature of the organic material, the curing time and the level of pressure applied during the cure. In other words, domain formation and sintering are kinetically directed processes. In an additional modality, the rate at which the sample is heated will affect the degree of domain formation and sintering. In total, processing conditions can be specifically chosen to obtain a conductive adhesive having the best combination of properties at minimum load, which often translates into lower cost and an opportunity to take advantage of other properties that are adversely affected by high loads. In some cases, when the adhesive is used in an application that is not able to withstand high sintering temperatures, higher pressures or non-traditional sintering techniques can be used to obtain exceptionally high conductivities. [0039] The filler component and the reactive organic compounds are chosen in order to create a homogeneous mixture when mixed. However, during curing, it is believed that the resulting polymer formed from the organic compound then has a repulsive interaction with the charge in order to allow the composition to self-assemble on the heterogeneous compound having rich domains where the charge composition is significantly greater than the charge concentration of the mass. In this way, while the general charge concentration (mass) of the compound does not change, the charge particles and the organic component perform self-assembly in situ in the respective regions of high concentration. This phenomenon can lead to a self-assembled network of charge particles Petition 870190126679, of 12/02/2019, p. 22/58 14/45 interconnected formed in situ from a mixture having very few, if any, initial charge-charge contacts. [0040] There are several approaches that can be employed to create the repulsive interaction between the charge component and the organic compound. However, in a preferred embodiment of the present invention, this is achieved by coating a charge particle with a non-polar coating and mixing the coated charge in a reactive organic compound comprising a relatively non-polar resin and a polar curing agent. In an uncured state, the resin, dressing and filler form a relatively homogeneous mixture where the coated filler and resin are compatible with each other and form a relatively homogeneous mixture. However, with the application of heat the curing agent reacts with the resin to form a polymer having polar portions in it, resulting in a repulsive interaction between the non-polar coating on the charge and the polar portions in the polymer. This repulsive interaction leads to self-assembly of polymer-rich and load-rich domains whose respective concentrations are significantly higher than the concentrations of the polymer mass and charge, respectively. In addition, extensive domain formation is capable of creating continuous charge-rich domains with particle contact with substantial particle between most particles in the charge. [0041] Other types of interactions capable of creating repulsive effects when curing the organic compound in the presence of the charge would consist, but are not limited to, electrostatic interactions, hydrogen bonding interactions, dipole-dipole interactions, induced dipole interactions, hydrophobic hydrophilic interactions , Van der Waals interactions and metallic interactions (as with an organometallic compound and metallic charge). Other forms of repulsive interactions could arise from related entropic effects such as differences in molecular weight in the polymers formed from the organic compound (s). Still, interactions Petition 870190126679, of 12/02/2019, p. 23/58 Repulsive 15/45 could arise as a result of an external stimulus such as an electric field. [0042] The domains formed when curing the organic compound in the presence of the filler result in domains rich in filler having filler concentrations greater than that of the mass (average) and in rich organic domains having lower concentrations of the filler (average) ). Areas of greater than average charge concentration may form semicontinuous or continuous courses of conductive charge material extending through the body of the cured composition. These courses provide a low-resistance pathway through which electrons and / or phonons can travel. In other words, the courses or channels allow for greatly increased thermal or electrical conductivity. This conductive stroke can be further increased by sintering the charge particles together. Such highly conductive strokes are particularly beneficial for LSP given the large amount of electrical current and heat that must be dissipated during a stroke event. [0043] Sintering, as is understood in the art, is a phenomenon of surface melting where particles are melted together at temperatures below the melting temperature of the material mass. This behavior is caused by a tendency of the material to relax to a lower energy state. In this way, selection of the type of load, size and shape can greatly affect the sintering capacity of the load particles. Certain particles, such as thin, wide, flat plates, are often formed by shearing large particles through various milling processes. This process provides a great deal of internal stress in addition to creating a great deal of surface area. When a certain amount of heat is added to the particles, they will tend to melt and melt together in this way, relieving the internal current and decreasing the general surface energy of the particles. Petition 870190126679, of 12/02/2019, p. 24/58 16/45 particles. For this reason, the preferred charge particles for use in the present invention are those that comprise some degree of thermal or electrical conductivity and sinter easily. In a further embodiment of the present invention, the preferred filler comprises a metallic particle that has been subjected to cold work that has provided current in the filler structure that still allows sintering. [0044] The sintering temperature will vary according to the material chosen as the filler, as well as the geometry of the filler particle. However, in a preferred embodiment of the present invention, it is advantageous to balance the curing of the organic compound and the sintering of the filler so that they occur simultaneously. In this modality, the temperature and the curing profile are selected to match the sintering temperature of the filler, so that the organic compound becomes repulsive to the filler and the filler particles are forced together, the individual filler particles can sinter. once particle to particle contact has been made. This is believed to be responsible for the continuous charge structure seen in the fully cured composition. In a preferred embodiment of the present invention, the sintering temperature is at least about 100 ° C, more preferably about 150 ° C and most preferably above 150 ° C for a silver sliver charge. [0045] In another embodiment of the present invention, a low temperature cure may be desirable. For example, when coating / applying the curable composition to a heat sensitive substrate, the curing agent and curing mechanism can be made especially to obtain a self-assembled, cured material at temperatures below 50 ° C and alternatively below temperature room (20-25 ° C). In embodiments of the present invention where sintering does not occur during a curing step, for example, in a low temperature curing environment, the particles may initially form courses Petition 870190126679, of 12/02/2019, p. 25/58 17/45 self-assemblies that are not sintered. A sintering step can then be added later. This subsequently added sintering step may comprise heating the self-assembled, cured material, or through space heating or electrically induced heating such as by lightning. [0046] In embodiments of the present invention, the self-assembling composition can be cured without the addition of heat. However, in a preferred embodiment of the present invention, the composition is cured by applying heat to the composition. Heat curing is generally performed in a curing oven such as a convection oven or an autoclave, with which hot air or radiated heat is used to increase the temperature of the composition. In alternative embodiments of the present invention, other curing methods can be employed such as induction curing in an electromagnetic field, microwave curing, infrared curing, electron beam curing, ultraviolet curing and visible light curing. In addition, the healing reaction can be self-accelerating through the use of an exothermic healing reaction. A non-thermal cure may be desirable, for example, when the composition is coated on a temperature sensitive substrate such as plastic. [0047] In one embodiment of the present invention, the charge comprises inorganic charges. Available fillers include pure metals such as aluminum, iron, cobalt, nickel, copper, zinc, palladium, silver, cadmium, indium, tin, antimony, platinum, gold, titanium, lead and tungsten, metal oxides and ceramics such as oxide aluminum, aluminum nitride, silicon nitride, boron nitride, silicon carbide, zinc oxide. Carbon-containing fillers could consist of graphite, carbon black, carbon nanotubes and carbon fibers. Suitable loads further comprise alloys and combinations of the loads mentioned above. Additional fillers include inorganic oxide powders such as fused silica powder, oxides of Petition 870190126679, of 12/02/2019, p. 26/58 18/45 alumina and titanium and aluminum nitrates, titanium, silicon and tungsten. Particle materials include versions having particle sizes ranging from a few nanometers to tens of microns. [0048] In one embodiment of the present invention, the charge is present at about 40 percent by volume or less, based on the total volume of the cured composition. In a more preferred embodiment of the present invention, the charge is present at about 30 volume percent or less, based on the total volume of the cured composition. In a more preferred embodiment of the present invention, the charge is present at about 15 volume percent or less, based on the total volume of the cured composition. [0049] In a preferred embodiment of the present invention, the charge comprises a material that is either electrically conductive, thermally conductive, or both. Although metals and metal alloys are preferred for use in various embodiments of the present invention, the filler may comprise a conductive sinterizable non-metallic material. In an alternative embodiment of the present invention the charge can comprise a hybrid particle where a type of charge, for example, a non-conductive charge, is coated with a sintering, conductive material, such as silver. In this way, the overall amount of silver used can be reduced while maintaining the sintering capacity of the charge particles and the conductivity of the sintered material. [0050] In one embodiment of the present invention, the filler component must be able to interact with the organic compound to provide a heterogeneous structure in the finished material. In a preferred embodiment of the present invention as discussed above, this is accomplished by interacting a polar organic compound with a non-polar charge. For preferred charge materials, such as metals, the charge is coated with a material comprising the desired degree of polarity. In a preferred embodiment of the present invention, the Petition 870190126679, of 12/02/2019, p. 27/58 The load coating comprises a coating of non-polar fatty acid, such as stearic, oleic, linoleic and palmitic acids. In a further embodiment of the present invention, the filler coating comprises at least one of several non-polar materials, such as an alkane, paraffin, saturated or unsaturated fatty acid, alkene, fatty esters, waxy coatings or oligomers and copolymers. In additional embodiments of the present invention, non-polar coatings comprise organotitanates with hydrophobic filaments or silicon-based coatings such as silanes containing hydrophobic filaments or functional silicones. [0051] In a further embodiment of the present invention, the coating (or surfactant, coupling agent, surface modifier, etc.) is applied to the filler particle prior to incorporating the particle into the curable composition. Examples of coating methods are, but are not limited to, deposition of the coating from an aqueous alcohol, deposition from an aqueous solution, deposition from the crude mass under load (for example, using a spray solution and a cone mixer, mixture of the coating and the load in a grinder or Attritor) and vapor deposition. In an additional embodiment, the coating is added to the composition to treat the load prior to the reaction between the organic components (namely the resin and dressings). [0052] In an alternative embodiment of the present invention, the charge / coating and polymer polarities are coated where the charge / coating comprises a polar portion and the organic compound comprises a non-polar polymer. Similarly, in an embodiment of the present invention, where a repulsive effect other than polarity is employed to direct self-assembly, the active properties of the charge and organic components can be interconnected. [0053] In a preferred embodiment of the present invention the compound Petition 870190126679, of 12/02/2019, p. 28/58 20/45 organic comprises an epoxy resin and a curing agent. In this embodiment, the organic compound comprises from about 60 to about 100 volume percent of the total composition. In this embodiment, the organic compound comprises approximately from 70 to 85 percent by weight of a diglycidyl ether of a bisphenol compound, such as bisphenol F, and 15 to 30 percent by weight of a curing agent, such as a polyamine anhydride based on the reaction between phthalic anhydride and diethylenetriamine. [0054] In further embodiments of the present invention, suitable organic compounds comprise monomers, reactive oligomers or reactive polymers of the types that follow siloxanes, phenolics, novolac, acrylates (or acrylics), urethanes, ureas, imides, vinyl esters, polyesters, resins of maleimide, cyanate esters, polyimides, polyureas, cyanoacrylates, benzoxazines, unsaturated diene polymers and their combinations. The curing chemistry would be dependent on the polymer or resin used in the organic compound. For example, a siloxane matrix may comprise a curable addition reaction matrix, a curable condensation reaction matrix, a curable peroxide reaction matrix or a combination thereof. Selection of the curing agent is dependent on the selection of filler component and processing conditions as shown here to provide the desired self-assembly of filler particles in conductive strokes. [0055] In another modality, due to its isotropic nature, the composition is conductive in all orthogonal directions, thus leading to significantly improved electrical and thermal conductivities in the z direction of composite structures. In turn, this improvement allows a considerable reduction in capacitive and heat formation effects associated with non-conductive resin layers present in composite laminates, as well as existing and similar LSP and EMF systems. Furthermore, the material can facilitate heat and electron transfer through the formation of carbon fiber bridges Petition 870190126679, of 12/02/2019, p. 29/58 21/45 adjacent within or between the layers of the composite substrate. In a further embodiment of the present invention, the highly conductive isotropic nature of the self-assembled material allows it to be subjected to quantitative non-destructive testing discussed in more detail below. [0056] Still, the self-curing self-assembly composition (stage A or stage B, but not stage C) has desirable handling properties and is easily adaptable to various forms of application. In one embodiment of the present invention, the self-assembling composition comprises a fluid adhesive (e.g., liquid or paste) that is capable of binding to a reactive or non-reactive substrate during curing of organic compound. In this way, the self-assembly composition comprises adhesive qualities that enhance certain application techniques and allow for stronger mechanical connections to substrates that in turn increase the electrical connections between the substrate and the conductive network within the adhesive. The result is an adhesive capable of bonding two adjacent surfaces together while providing additional protection against LSP. [0057] In a further embodiment of the present invention, the self-assembly composition is provided as a two-part system where the curable organic component is present on one side A and the curing agent is present on one side B, so that, when mixed, the curing reaction is initiated. The load and any other optional components can reside on either side A, side B, or both. [0058] In another embodiment the composition is in the form of a stage B film adhesive that is generally used in composite applications. In addition, the film adhesive has optional carrier fabric, such as a non-woven cover to enhance handling properties. In yet another modality, the cover can be electrically conductive to further improve the Petition 870190126679, of 12/02/2019, p. 30/58 22/45 composition protection ability against LSP. [0059] In another embodiment of the present invention, the composition can be applied as a spray to a substrate by adding a solvent to the composition. In a preferred embodiment of the present invention, the solvent comprises a structure suitable for dissolving (in whole or in part) the organic compound while being capable of being evaporated under common processing conditions for composite structures. In a preferred embodiment of the present invention, where an epoxy resin is employed, the solvent comprises, but is not limited to, acetone, methyl ethyl ketone, toluene, xylene, benzyl alcohol, butyl acetate, cyclohexanone, dimethoxyethane, trichlorethylene, glycol ethers and mixtures thereof. In addition, the choice of solvent will also be dictated by the dressing used. In a preferred embodiment, it is desirable to select a chemical agent such as acetone that acts as a solvent for the epoxy resin and a non-solvent for the polyamine anhydride adduct. In a preferred embodiment of the present invention, the solvent comprises 0.25 to 1.5 part by weight of the non-solvent components. [0060] In another embodiment of the present invention, the composition is used in conjunction with fiber reinforcement (e.g., fibers, fiber bundles, woven fibers or fabrics and the like) to produce coated or pultruded fibers, composite prepegs, tapes and the like . In other words, the composition acts as the traditional resin component used to form traditional prepreg and related materials. In an additional embodiment, the self-assembled material discussed here is condescending and facilitates many known manufacturing techniques including infiltration techniques such as resin transfer molding, resin film infusion and vacuum assisted resin transfer molding, etc. [0061] In an additional embodiment of the present invention, the self-assembly composition can be used to produce a structure Petition 870190126679, of 12/02/2019, p. 31/58 23/45 laminated with two or more layers so that the upper layer comprises the conductive self-assembly composition and the base layer (s) is comprised of lighter weight electrically conductive resin, and / or a non-conductive resin such as a traditional surface film. In addition, non-conductive resin can be mentioned, the laminated structure gives increased surface conductivity while maintaining a given weight relative to a monolithic film of lower surface conductivity. In addition, the thickness of each layer can be varied to further increase surface conductivity while maintaining a given weight. [0062] In yet another embodiment of the present invention, the uncured composition is employed in combination with an existing LSP protection system to create a unique hybrid structure in this way producing attractive combinations of protection against LSP and weight. Examples include, but are not restricted to, the self-assembling material used a B-stage film to fit solid metal sheets, EMFs, metallized fibers, metallized woven, metallized non-woven fibers (eg coverings), or fiber joints of carbon-metal. [0063] The methods and materials of the modalities of the present invention can be used to provide lightning protection to a variety of substrates, parts, machines, vehicles and apparatus. In a preferred embodiment of the present invention, the methods and materials of the present invention are employed to provide LPS to vehicles, including aircraft, marine and land vehicles, as well as structures such as antennas, radars and wind turbines. [0064] With reference to figure 1, an example of substrate in one embodiment of the present invention is provided as is generally found in commercial composite applications such as those involved in the aerospace industry. The substrate in figure 1 is comprised of a laminated type structure Petition 870190126679, of 12/02/2019, p. 32/58 24/45 sandwich where multiple layers of structural carbon fiber prepeg 4-6 and 10-12 intersect with a light weight, inner bee house core 8, with layers of adhesive film 7 and 9 adhering to the joint assembly. The LSP 3 system is applied to the upper part of the upper carbon sheets 4-6. It should be noted that commercial LSP systems often have a fiberglass insulation sheet that is sometimes used to prevent galvanic corrosion that occurs between carbon fiber substrates and metals in the LSP system (especially those that have galvanic potential. different from that of carbon). The self-assembling material of an embodiment of the present invention 3 provides LSP and is subsequently coated with protective and decorative paint layers of primer 2 and coating 1. In alternative embodiments of the present invention, monolithic structures, that is, those based only on prepegs of fiber, are also commonly found. Prepegs and related fiber reinforce resins that can consist of several different shapes such as woven fibers embedded in resin, unidirectional fibers within a resin (for example, in the form of a large sheet or ribbon) or pultruded fibers that are impregnated with a resin . Fiber reinforcement can consist of many different types of fibers and many fiber configurations such as fibers made of glass, carbon, boron, aramid, silicon carbide, etc., and fiber configurations such as unidirectional bundles or woven fabrics. In addition, as previously mentioned, the self-assembling material of the present invention can be used with resin component traditionally used to form resin prepegs, pultruded bundles and the like. In another embodiment, the substrate may be comprised of fiber reinforcing plastic. [0065] In another embodiment of the present invention, due to the ability of the organic component to react and form covalent bonds, it can be easily cured with or cured on reactive or non-reactive substrates (for Petition 870190126679, of 12/02/2019, p. 33/58 25/45 example, thermoplastic or a previously reacted thermoset), respectively. Furthermore, proper selection of chemical resin potential allows the replacement of one or more layers typically found on the outside of the aircraft, such as primer and coating layers, used to paint the aircraft (ie layers 1 and 2 in figure 1 ). Furthermore, with appropriate load selection, the present invention is capable of providing performance against lightning and corrosion without the need for an insulation sheet. [0066] Also, due to its highly conductive isotropic nature, it is capable of being used as a multifunctional material for the purpose of lightning protection and, but not limited to, protection against electromagnetic fields caused by the indirect effects of lightning or man-made sources such as electronics and communications. In addition, the material can also serve to eliminate static charge formation through electrostatic dissipation or as a heat conduit for melting ice as part of a defrosting system. In addition, the multifunctional ability of the composition overcomes the issues of having to combine metallic structures, for example, EMFs, with adhesive films before their integration into the composite structure. [0067] In another embodiment of the present invention, the cured self-assembled material provides a clear course to the base along the outside of a composite aircraft or other substrate. This course for the base allows manufacturers to reduce the amount of wires in the base for electrical devices by using conductive material to complete a circuit. [0068] As previously mentioned, the fabrication of the LSP fiber prepeg substrate can be carried out by curing the materials together during typical composite processing techniques such as autoclave curing, autoclave curing or compression molding. Alternatively, the self-assembling adhesive could be cured after the Petition 870190126679, of 12/02/2019, p. 34/58 26/45 base have been healed. In addition, the self-assembling adhesive could be cured for the thermoplastic substrate. In an additional embodiment, increased pressure levels that are generally found in composite processing and curing can further assist in sintering the filler particles that occur following the self-assembly of the composition. Examples of composite applications include: wing and tail coverings, control surfaces, airfoils, antenna domes, helicopter blades, wind turbine blades, stringers, masts and supports. [0069] In another embodiment of the present invention, the self-assembling material can be used as an LSP adhesive to attach and / or seal a gasket, screw, fastener, rivet and the like. The material can provide both mechanical integrity and electrical continuity by joining sections to prevent bending in or around the joint. In a further embodiment of the present invention, the material serves to support the composite to a substrate, such as an airplane structure. [0070] As previously mentioned, EMFs are difficult to repair when damaged. The meshes and the damaged base structure must be carefully sanded and cut and replaced with new material. The difficulty in repairing arises in the union of new EMF with the existing one. It is essential that the new EMF aligns perfectly. If not, there are gaps that limit the electricity fluid in future lightning strikes; this can ultimately compromise the safety of the aircraft. In addition, the EMF can be easily deformed with simple handling. EMF is also known to cause surface defects in the painting process that require rework. It is for these reasons that care must be taken and time taken to ensure proper repairs using state of the art EMF materials. [0071] In an additional embodiment of the present invention, the material Petition 870190126679, of 12/02/2019, p. 35/58 27/45 self-assembly of the present invention is employed to repair surfaces damaged by lightning. This repair method overcomes the repair difficulties associated with sheet metal and other prior art systems. Due to the unique self-assembling conductive structure of the materials of the present invention, metal-to-metal interfaces do not require alignment since the self-assembling material will form interconnections in situ when the material is applied to a repair site. The particular means for employing the compositions of the present invention in a repair procedure includes spraying or painting the uncured material on the section to be repaired, or pre-forming a stage B or stage C sheet, then applying the sheet to the area damaged. [0072] In an embodiment of the present invention, a repair process includes the sanding steps of the panel to remove paint and expose the damaged area including the original conductive material (sheet metal, self-assembled conductive strokes, etc.), then cut around from the perimeter of the damaged area using a cut that penetrates through the bee house, removed from the carbon leaf and bee house, and sanding the top three layers of carbon leaf leaving a gradual structure. Then the bottom of the hole is lightly sanded with a pneumatic angle grinder, and the repair area is cleaned with oil-free compressed air. Then an adhesive film is applied to the sides and to the bottom of the hole in the bee house, a prefabricated bee house plug is applied to the repair and additional adhesive film is put on the bee house and the chamfered area, before the application of 3 sheets of carbon fiber prepeg according to the repair sizes, starting with the smallest. The self-assembling LSP material of one embodiment of the present invention is placed over the repair area so that it overlaps the existing LSP for electrical conductivity and the panels are placed on a release coated modeling face and a vacuum bag was built around them, and the assembly has excess Petition 870190126679, of 12/02/2019, p. 36/58 28/45 volume removed for about 20 minutes and then cured in an autoclave at 344.74 kPa (50 psi), 2 hours isothermal at 177 ° C, before lightly rubbing the panels with 240 grit sandpaper and cleaning with compressed air without oil and paint the panels with a primer and coating as desired. [0073] In an additional embodiment of the present invention, the self-assembling LSP material can be used to repair lightning protection systems of the prior art such as conductive expanded metal sheet, metal mesh, carbon-metal fiber joints, metallized carbon, metallized glass fiber or charged conductive polymer. The unique self-assembling material of modalities of the present invention allows easy application to a damaged area and automatic alignment with existing conductive strokes to form a continuous conductive course between the prior art system and the self-assembled repair material of the present invention. [0074] In a further embodiment of the present invention, the self-assembling conductive material allows the use of automatic manufacturing equipment for applying LSP to composite structures. Examples include, but are not limited to, applying the self-assembling material in the form of a spray using automatic spray equipment so that the sprayed material is applied to the outside of uncured fiber-reinforced polymer in a male mold structure or structure of female mold from the surface that has been pre-treated with a release agent. In addition, the self-assembling material could be applied in combination with multiple unidirectional filaments (for example, fiber or tape) using automatic tape or fiber laying machines. The ability to form continuous electrically conductive strokes following curing of adjacent filaments overcomes the aforementioned issues of fabrication and weight associated with prior art materials. [0075] In an additional embodiment of the present invention, the material Petition 870190126679, of 12/02/2019, p. 37/58 29/45 self-assembling conductor allows non-destructive inspection (NDI) of the material as applied to the surface. NDI techniques are critical in applications such as the manufacture of composite aerospace structures. NDI methods allow for significant savings in manufacturing time and cost while also allowing mission-critical structures to be made to the highest quality standards. The materials of the present invention allow simple quantitative non-destructive inspection techniques for external parts of LSP during the life of the external part. The cured LSP layer can be quickly inspected by contacting the surface with a standard electrical resistance probe, such as a 4-point probe. The electrical resistance values can then be related to performance with respect to the level of protection against lightning and protection against electromagnetic interference (EMI). The surface resistance is dependent on the volume of conductivity of the material as well as the thickness of the coating. [0076] In an embodiment of the present invention, the cured self-assembled coating is electrically conductive in all three dimensions (width, length and thickness). In this way, electrical resistance measurements can be easily made on the surface of the coating using a standard device such as a 4-point probe connected to an ohmmeter. [0077] Although the present invention has been described with reference to particular modalities, it should be recognized that these modalities are only illustrative of the principles of the present invention. Those of ordinary skill in the art will understand that the compositions, apparatus and methods of the present invention can be constructed and implemented in other ways and modalities. Accordingly, the present report should not be read as limiting the present invention, since other modalities also fall within the scope of the present invention as defined by the appended claims. Petition 870190126679, of 12/02/2019, p. 38/58 30/45 EXAMPLES [0078] The self-assembly lightning protection composition described in the Examples comprises diglycidyl ether of bisphenol F (DGEBF) resin (or a mixture of DGEBF with diglycidyl ether of dipropylene glycol), an amine adduct dressing based on the reaction with diethylene triamine and phthalic anhydride, and silver flake coated with stearic acid (surface area of about 0.8 m2 / g and weight loss in air at 538 ° C of about 03%), and optionally a solvent based on a mixture of toluene, methyl ethyl ketone, ethyl acetate and ligroin (35%, 32%, 22%, 11% by weight, respectively). [0079] These coatings were converted into several different application forms, applied and treated with a composite laminated structure (test panel) and tested for lightning performance. These LSP materials and methods ultimately provided protection against lightning strikes because of their ability to form continuous, highly conductive electrical courses in all orthogonal directions. In other words, the ingredients of the materials self-assemble to form a three-dimensional mesh during curing of the material. In addition, these materials allow direct and indirect protection in state-of-the-art expanded sheet metal protection systems. Finally, self-assembling LSP materials of the modalities of the present invention have the potential to overcome many of the issues encountered with state of the art materials such as handling, processing, automation, repair, among other issues mentioned above. Below is a list of Supporting Examples preceded by the description of materials, panel construction and lightning test conditions. [0080] Figure 1 shows the cross section of the laminated test panels used for testing different lightning systems described here. The laminate configuration was chosen to represent the type of construction that Petition 870190126679, of 12/02/2019, p. 39/58 31/45 can be found in fixed and / or rotary wing aircraft. The construction is also similar to composite laminates used in composite blades for wind turbines and helicopter blades, both of which are susceptible to lightning. Table 1 lists the materials used to build the panels. Details of the LSP systems used are described below. Table 1. List of materials used to prepare lightning test panels Material Layer No.in figure 1 description Urethane Coating 1 Aerospace grade urethane paint PPG CA80000 C5 Epoxy Primer 2 PPG 515-349 aerospace grade sandable epoxy primer LSP system 3 See Specific Examples Prepeg ofCarbon 4-6, 10-12 Heatcon® (HCS2402-050) 3k-70E Flat Wave Carbon Fiber Epoxy Adhesive Film 7.9 Heatcon® Epoxy Adhesive Film (HCS2404-050) Bee house 8 Nomex bee house, thickness 9.52 mm (3/8), cell 3.18 mm (1/8) [0081] Composite panels, 60.9 cm, 60.9 cm x 1.27 cm (24 in. X 24 in. X% in.), Were constructed using the general procedure described below. The materials were first cut into 60.9 cm x 121.8 cm (24 in. X 48 in.) Formats. Layers 3-6 and 10-12 (see figure 1) were stretched separately by hand, vacuum packed and excess volume removed under vacuum to remove trapped air and ensure close contact between adjacent sheets. The two laminates were then removed from the pouch and combined with the bee house core material (layer 8). The resulting laminate was contained in support structures of 60.9 cm x 121.8 cm (24 in x 48 in) that were adhered to an aluminum table top (modeling surface). The aluminum table top was treated with Petition 870190126679, of 12/02/2019, p. 40/58 32/45 a Frekote® mold release agent before stretching the materials. The lightning protection layer (LSP) (layer 3) was oriented face down against the modeling surface. The multilayer laminate was covered with release film, drainage fabric and vacuum packaging film. The packaging film was adhered to the modeling surface with mastic tape. Vacuum was applied to the pouch for ~ 20 minutes before autoclaving. The entire laminate-modeling assembly was placed in an autoclave, equipped with vacuum connections, and cured using the following conditions: Evolution: 1.25 ° C / minute (2 ° F / minute), that is, ~ 2 h for temp Soak: 179 +/- 6 ° C (355 +/- 10 ° F), 2 hours Pressure: 3.40 atm (50 psi) Cooling: Max 3.75 ° C (6 ° F / min) to 27 ° C (80 ° F) over the course of ~ 45-60 min Cooling with air overnight under static vacuum. [0082] The cured panels were removed from the vacuum bag / mold assembly and cut to 60.9 cm x 60.9 cm (24 in. X 24 in. Panels). Each panel was painted with an epoxy primer and urethane coating paints. Before painting, the surface of each panel was lightly sanded with 240 grit sandpaper. Masking tape was applied to the outer 2.54 cm (1 in.) Edge of the panel. The epoxy primer (layer 2) was then applied to a wet film and directed dry thicknesses of 38 microns (0.0015 in.) And 19 microns (0.00075 in.), Respectively. The primer was allowed to dry for a minimum of 2 hours before applying the urethane coating (layer 1). The urethane coating was applied in two applications. The first application was aimed at a wet film thickness of 50 microns (0.002 in.). The second application was targeted at a thin film thickness of 64 microns (0.0025 in.). Approximately 7-13 minutes were allocated for drying time between the first and second Petition 870190126679, of 12/02/2019, p. 41/58 33/45 applications. The panel was left to dry for a minimum of 2 hours before handling. Additional details on how the various LSP materials were prepared and incorporated into the laminates were described in the Examples below. [0083] The Zone 1A and Zone 2A lightning test was conducted in accordance with SAE ARP5412. The panels were positioned ~ 2.54 cm (1 inch) below the emission electrode. Grounding strips were positioned and secured with C clamps along the 2.54 cm (1 inch) unpainted perimeter of the panel. Visual inspection was done on all panels following the test. The extent of damage was quantified in terms of the extent of lightning penetration and damage to the surface area. EXAMPLE 1 [0084] Table 2 compares the lightning results from Zone 1A for various LSP systems (pictorially represented by Layer 3 in figure 1). Specific details of the various panels and corresponding LSP systems are as follows: Panel A did not contain any lightning protection system, that is, Layer 3 (see figure 1) was absent during the construction of the panel. Panels B and C (State of the Art) were comprised of Aluminum and Copper Expanded Metal Sheets (EMF) which were supplied pre-soaked in a surface adhesive film (SG4528-016AL-104V and SG4528-04CU103V, respectively, of APCM-AME, Planfield, Connecticut) which was further combined with a fiberglass insulation sheet (FGF108-29M-990, Toray Composites America, Inc.). The insulation sheet was located between the EMF adhesive film and the upper carbon fiber layer (Layer 4 in figure 1). Ref1 and Ref2 provided additional EMF data previously reported by Welch and others at Spirit AeroSystems (SAMPE Journal, Vol. 44, July 4 / August 2008, pp. 6-17). The panels described in this report are very similar in construction to those built for the present Examples (see figure 1). The LSP system Petition 870190126679, of 12/02/2019, p. 42/58 34/45 for Ref1 has the same configuration as Panel A, that is, an aluminum EMF embedded in a surface film (Surface Master 905) that was stretched over a fiberglass insulation sheet (Style, 1581, glass S2). The LSP for Ref2 consisted of copper EMF embedded in a surface film (Surface Master 905). Remember that Ref2 does not contain a sheet of glass insulation, unlike Panels B, C and Ref1. [0085] The D-F panels were based on self-assembling materials of an embodiment of the present invention. The LSP materials for panels D and E were formed in adhesive films based on the resin, dressing and filler mentioned above. Specifically, both films were prepared as follows: Adhesive pastes comprising 17.8% by weight of diglycidyl bisphenol ether F, 6.8% by weight of amine adduct dressing and 75.4% by weight of flake silver (25% by volume) using a Hauschild, double-acting centrifugal mixer. [0086] These pastes were then stretched into films of 66.0 cm x 66.0 cm (26 in; x 26 in.) Nominally 50 microns thick. The film was stretched using a 71.1 cm x 68.6 cm (28 in. X 27 in.) Mirror surface which was covered tightly with fluoropolymer release film (Airtech WL5200 0.002 in.). Strips of brass foil, 50 microns thick (0.002 in.), Were placed on two outer edges of the mirror to control the thickness of the film. Nominally, 200 grams of the self-assembling adhesive were applied to the release film in two beads the width of the released film surface. A custom-made aluminum stretch bar, 68.6 cm (27 in.) Wide x 3.8 cm thick (1.5 in.), Was slowly moved by hand, under pressure, across the surface of the release film towards the opposite end. As the bar passed over the conductive paste beads, the paste was stretched into a uniform film. The thickness of the film Petition 870190126679, of 12/02/2019, p. 43/58 35/45 was governed by the thickness of the brass sheet strips. Various stretches using the stretch bar were required until the desired film thickness and uniformity were achieved. [0087] Once the adhesive film has been stretched, an upper release film has been applied for protection. The entire 3-layer laminate (release film, conductive film and top release film) was passed through a slip roller to improve any irregularities in the film. The laminate film was then placed on a sheet metal substrate and partially cured (Stage B) in an oven preheated to 85 ° C for 13 minutes. After stage B, the film was cohesive, although flexible, and the upper release film could be removed without causing damage. Stage B films were stored at -20 ° C or below until needed for stretching and curing of test panels. [0088] Panel F is a spray version of an LSP self-assembling adhesive according to an embodiment of the present invention. Conductive paste was prepared in the same way as above using the following ingredients: 6.5% by weight of diglycidyl ether of bisphenol F, 6.5% by weight of diglycidyl ether of dipropylene glycol, 4.8% of adduct dressing amine and 82.24% by weight of silver flake (33% by volume). The pastes were mixed by hand with a solvent mixture comprising 36% toluene, 32% methyl ethyl ketone, 22% ethyl acetate, and 10% ligroin, by weight, in a ratio of approximately 1 part solvent for 2 parts of paste by weight. The mixture was spray-coated on uncured laminated panels using an HVLP spray gun. The resulting material was loaded onto the HVLP spray gun (air ~ 103.42 - 206.84 kPa (~ 15 - 30 psi), 1.4 mm tip) and applied to the uncured fiberglass insulation sheet ((FGF108-29M-990, Toray Composites America, Inc.) supported by three carbon sheets not cured by Petition 870190126679, of 12/02/2019, p. 44/58 36/45 low (Layers 4-6) at a distance of 20-30 cm (8-12 in.) From the surface. The coating thickness was approximately 107 microns (0.0042 inches). The substrates were allowed to dry under ambient conditions for a minimum of 10 minutes and then cured under the conditions mentioned above. [0089] Before discussing the results, it is important to comment on the basic criteria for protection against lightning. The basic criterion for LSP is the prevention of catastrophic effects, that is, effects that compromise the safety of the aircraft that prevent it from landing safely. From a structural point of view it is desirable to preserve the base composite substrate following lightning. Ideally, minimal breakage of none of the fibers within the composite laminate substrate is preferred. Still, it is desirable, although not critical, to have minimal cosmetic damage to the painted surface. Minimizing the burning or scorched area will minimize the amount of materials and time required for subsequent repair of the damaged surface. With that in mind, the panels in these and subsequent Examples have been inspected for structural damage, that is, damage to carbon sheets, and cosmetic damage, extension of the burning or scorched area. [0090] Also, the action integral measured during the lightning test is also reported. By SAE ARP5412, the action integral is related to the amount of energy absorbed and is a critical factor in the extent of damage. The action integral for Zone 1A tests must be 2x106 A2s (+/- 20%). Considerable deviation below this value under equal test conditions indicates significant absorption of energy which is often reflected in physical damage to the test specimen, for example, burning, punctures, etc. [0091] The results in Table 2 show degree of protection or variable damage to blows in Zone 1A depending on the choice of the LSP system. Panel A, having no coup protection, exhibited catastrophic failure. The lightning Petition 870190126679, of 12/02/2019, p. 45/58 37/45 penetrated all six carbon sheets on the panel; in this way resulting in a large orifice and extensive firing damage. In addition, the action integral fell below the accepted level, which is an additional indication of significant hit energy absorption and the material's inability to properly ground the current. [0092] All state-of-the-art EMF systems (Panel B, Panel C, Ref1 and Ref2) prevented lightning from penetrating the base carbon structure with varying degrees of surface damage or cosmetic damage. Panels B and C exhibited a comparable amount of surface / cosmetic damage to be expected given their very similar constructions. Also, the level of damage to the surface is considerably less than that observed for the copper, Panels C and Ref2 systems. This result is mainly due to the smaller volume of metal within the LSP system due to the denser copper. As expected, the heavier copper system (Panel C) outperforms Ref2 because of the larger amount of copper in Panel C's LSP system. Understandably, all action integrals were in specification due to the proper LSP. [0093] Similar to the EMF systems of the prior art, panels based on the materials and methods of the present invention including a self-assembling material containing conductive strokes prevented the penetration of lightning into the base structure and in turn acceptable action integrals. This is true for both film and material spray versions. Panel D, a film version of the self-assembled material accompanied with an insulation sheet, exhibited performance and weight levels close to those of the copper / surface film used in Panel Ref2. Removing the insulation sheet in the heterogeneous film (Panel E) provides protection in substantially reduced weight with respect to the state-of-the-art EMF systems. Specifically, Panel E Petition 870190126679, of 12/02/2019, p. 46/58 38/45 prevents damage to the carbon substrate by ~ 22% less weight than lighter EMF comparisons (Panels B and Ref2). Panel F demonstrates that spraying a conductive coating directly onto the carbon prepeg followed by co-curing is capable of providing direct protection against simulated lightning in Zone 1A, that is, any carbon sheets have been penetrated. Table 2. Summary of Results for Zone 1A Lightning Tests Panel Name LSP System (Area Weights, g / m 2 ) Total Area Weight of LSP System, g / m 2 Number of Penetrated Carbon Sheets Surface Damage (b) , cm Integral of Action, x10 6 A 2 .s No LSP Protection THE none 0 6 24 1.42 State of the Art Expanded Metal Mesh Systems B Al (78) + Isoply (82) + Surface Film (171) 331 0 23 2.04 Ç Cu (195) + Isoply (82) + Surface Film (181) 458 0 28 2.08 Ref1 (a) Al (78) + Isoply (82) + Surface Film (171) 331 0 14 AT Ref2 (a) Cu (78) + Surface Film (171) 313 0 29 AT Self-Assembly LSP Materials D FilmStraight (261) + Isoply (82) 343 0 35 1.90 AND Film 257 0 23 1.97 Petition 870190126679, of 12/02/2019, p. 47/58 39/45 Straight (261) F Straight Spray (452) + Isoply (82) 532 0 19 2.08 (a) Ref1 and Ref2 are test results based on Zone 1A for EMF LSP systems previously reported by Welch and others from Spirit AeroSystems (SAMPE Journal, Vol. 44, No. 4, July / August 2008, pp. 6 -17). The panels described in this report are very similar in construction to those listed in the rest of Table 1. Additional details can be found in the descriptive text of the examples in the referred article. (b) The damage to the surface corresponds to the diameter of the circular area that was cosmetically damaged by carbonization, burning or evaporation of paint and / or resin. EXAMPLE 2 [0094] Table 3 compares the hit results from Zone 2A for various LSP systems (pictorially represented by Layer 3 in figure 1). Panel G (State of the Art) was comprised of aluminum EMF (Grade 016, Pacific Coast Composites) which was combined with a film adhesive (HCS2404-050, 242 g / m2, Heatcon® Composites) which was further combined with a fiberglass insulation sheet (FGF108-29M-990, Toray Composites America, Inc.). The insulation sheet was located between the EMF adhesive film and the upper carbon fiber layer. Panel H was prepared in the same way as Panel F except for the use of the following ingredients for the mixture of conductive paste and solvent. Conductive paste: 25.1% by weight of diglycidyl ether of bisphenol F, 9.6% by weight of amine adduct dressing and 65.3% of silver flake (17% by volume). Solvent mixture: acetone 50%, toluene 18%, methyl ethyl ketone 16%, ethyl acetate 11% and ligroin 5% by weight. [0095] Although both panels in Table 3 prevent failure Petition 870190126679, of 12/02/2019, p. 48/58 40/45 catastrophic and demonstrate acceptable Action Integrals (ie 0.25 +/- 20%), Panel G based on aluminum EMF exhibited damage to the first carbon fiber sheet. In contrast, no penetration of carbon sheets was observed for panel H based on the self-assembling material of an embodiment of the present invention. In addition, the area weight was half that of the comparison. This performance of the present invention derives in part from the isotropic nature that allows very high conductivity in the z direction in addition to the x & y directions. Table 3. Summary of Results for Zone 2A Lightning Strike Tests Panel Name (Figure No.) LSP System (Area Weights g / m 2 ) Total Area Weight of LSP System (g / m 2 ) Number of Penetrated Carbon Sheets Surface Damage (a) , cm Integral of Action, x10 6 A 2 .s State of the Art Expanded Metal Mesh Systems G Al (78) + Isoply (82) + Surface Film (242) 404 1 6 0.28 Heterogeneous LSP Materials H PulverizationStraight (202) 202 0 12.5 0.26 (a) The surface damage corresponds to the diameter of the circular area that was cosmetically damaged by carbonization, burning or evaporation of paint and / or resin. EXAMPLE 3 [0096] As previously mentioned, the self-assembling nature of the materials of the present invention has the ability to form continuous, conductive strokes during material curing. This feature is especially unique since it allows a person to form a bridge Petition 870190126679, of 12/02/2019, p. 49/58 41/45 electrically between interfaces (for example, a union between two adjacent sections) that are generally found in the original construction of structures and during the repair of existing ones. In addition, this method allows a person to automate the LSP manufacturing process. State-of-the-art materials based on sheet metal do not have the ability to form continuous interfaces at the joint, which often leads to very large electrical resistances through the interfaces between separate LSP EMFs. In addition, automated LSP is prohibitive due to issues of union, issues of fragility and weight. [0097] To illustrate the ability of the present invention to bridge electrically between interfaces, the same self-assembling LSP material for Panel H was spray-coated onto two different 10 cm x 30 cm sheets (3.9 in. X 11 , 8 in.) Of carbon fiber prepeg (3k-70 PW Carbon Fiber Epoxy). The resulting coating was approximately 75 microns (0.003 in.) Thick. The two coated sheets were then joined on a metal shaping surface (coating against the surface), thereby creating a linear defect along the interface of the two samples. Two 20 cm x 30 cm (7.9 in. X 11.8 in.) Carbon fiber sheets were applied to the back of the bonding sheets. The entire structure was then vacuum packed and cured at 177 ° C (350 ° F) for 3 hours. Electrical resistance measurements were made using a 2x2-point probe with 7 cm probe spacing within each original coating and through the tip joint. The cured coating exhibited comparable electrical conductivity through the initial tip seam defect as measured through each of the original samples. This is attributable to the unique structure of the material that allows self-assembling conductive strokes to form electrical connections with the existing LSP system. Table 4. Values of electrical resistance for joined carbon panels based on heterogeneous conductive coatings / self-assembly Petition 870190126679, of 12/02/2019, p. 50/58 42/45 Panel Location Electrical Resistance (a) (mOhms) Inside the Left Laminate 91.1 Inside the Right Laminate 91.1 Through the original end joint of two laminates 88.9 (a) Electrical resistance was measured using a 2x2 four-point probe with a 7 cm probe-to-probe spacing. EXAMPLE 4 [0098] Composite sandwich panels that were previously hit by Zone 1A simulated lightning were used as test specimens. Two types of panels were used: Panel G based on expanded copper foil (state of the art) and Panel H based on self-adhesive adhesive coating. Both panels were repaired according to FAA approved methods using a step-sand approach (DOT / FAA / AR-03/74). Both panels were repaired with a spray solution based on the self-assembly spray adhesive mentioned above in Example 1. The solvent mixture was loaded onto the HVLP spray gun (air 103.42 - 206.84 kPa (15-30 psi), 1.4 mm tip) and applied to the repaired panels. [0099] Specific details of the entire repair process are as follows: The panels were sanded with a double orbital sander to remove paint and expose the damage. This sanding also exposed the copper EMF in the case of Panel G, which allowed the self-assembling material to make electrical contact with the sheet. A circular cut that penetrated through the bee house was then made around the perimeter of the damaged area. The carbon leaves and the bee house were removed. The bottom of the hole was then lightly sanded with a high speed pneumatic angle grinder. The top three layers that were carbon were then sanded in this way leaving a staggered structure. The pitch was 1.27 cm / sheet. The repair area was then blown with compressed air Petition 870190126679, of 12/02/2019, p. 51/58 43/45 without oil. Then, adhesive film (see Table 1) was applied to the sides and bottom of the hole in the bee house. A cap and bee house was manufactured and applied to the repair. Adhesive film was put on the bee house and the area chamfered. Three sheets of carbon fiber prepeg (see Table 1) of size compatible with the steps were applied to the repair, starting with the smallest. The self-assembling adhesive spray solution was sprayed over the repair area so that it overlapped the existing LSP for electrical conductivity. The panels were placed on a molded release-coated face and a vacuum bag was built around them. The assembly had excess volume removed for 20 minutes and then cured in an autoclave at 344.74 kPa (50 psi), isothermal 2 hours at 177 ° C. Following curing, the panels were lightly rubbed with 240 grit sandpaper and cleaned with airless compressed air. They were then primed and painted as previously described. [00100] The repaired panels were struck directly at the repair site with Zone 1A as previously described. Both repairs were able to adequately protect the composite panels without any significant structural damage to the panel. The damage was isolated to the buffer area in the form of carbonization and evaporated resin from the edges and upper carbon layer of the repair. In both cases the plug remains firmly in place after the stroke. The discoloration of the paint around the perimeter of the repair was mainly in the form of soot that was easily removed with cleaning. EXAMPLE 5 [00101] A self-assembling adhesive paste of the present invention was prepared using the following formulation: 25.3% by weight of diglycidyl bisphenol F ether, 9.7% by weight of amine adduct dressing and 65.0 % by weight of silver flake (about 17% by volume). The components were mixed until uniform in a Hauschild DAC 150 F mixer. Petition 870190126679, of 12/02/2019, p. 52/58 44/45 [00102] A solvent mixture was then mixed into the paste in a ratio of 1 part solvent mixture to 2 parts paste. The solvent mixture consisted of 50% acetone, 18% toluene, 16% methyl ethyl ketone, 11% ethyl acetate and 5% ligroin, by weight. [00103] The resulting ink mixture was quickly mixed manually followed by 5 minutes of mixing on a standard ink stirrer. The paint mixture was then filtered and loaded into a manual HVLP spray gun with a tip size of 1.4 mm and ~ 103.42 - 206.84 kPa (~ 15 - 30 psi), air pressure. The paint mixture was then sprayed onto a non-conductive G11 epoxy plate substrate. (The non-conductive substrate was chosen due to its transparency to electromagnetic waves that could allow measurement of the true protection effectiveness of the conductive coating). The coated substrate was then cured at 160 ° C for 1 hour. The sheet resistance of the cured film was on average 0.036 Ω / square as measured using a 4-point probe. The film thickness was approximately 50 microns (0.002 in.). The electromagnetic protection effectiveness of the coating was measured using a MIL-STD-285 procedure modified in plane wave at frequencies from 30 MHz to 12 GHz. It is important to note that the test results below 240 MHz are semi-quantitative since the port - 60.9 cm x 60.9 cm (24 in. X 24 in.) sample (opening) begins to block EM transmission as well. The results in figure 2 show that the coating based on the present invention is capable of providing high levels of protective effectiveness, that is, 50 dB and more, over a wide range of frequencies. EXAMPLE 6 [00104] The self-assembling LSP material according to an embodiment of the present invention was applied on sheets of commercial carbon fiber reinforced polymer (CFRP). The support structure under these sheets of Petition 870190126679, of 12/02/2019, p. 53/58 45/45 Surface CFRP was a Nomex® bee house core and additional CFRP sheets at the rear. These flat panels were autoclaved at 179 +/- 6 o C (355 +/- 10 ° F). The result was a fully cured CFRP bee house panel cut to 60.9 cm, 60.9 cm x 1.27 cm (24 in. X 24 in. X ~ 0.5) with an LSP coating on one surface. [00105] After curing, these flat panels approach a composite aircraft exterior structure before priming and coating. Electrical resistance measurements can be easily made on the surface of the LSP coating. These measurements can be spot tests using all 4 probe pins allocated together or distance tests where each pair of probe pins is spaced a given distance. The panels were then painted with aerospace grade primers and coatings and underwent Zone 1A lightning strike tests according to SAE 5412 specifications. [00106] Figure 3 shows how surface resistance can be used to predict performance of LSP which is a valuable method in assessing quality during fabrication and extent of damage after a hit or impact. In figure 3, the electrical resistance of the LSP coating is illustrated in a graph against the damage area of the same panel after the lightning strike of Zone 1A. The electrical resistance of the coating was measured with a 4-point probe point test. The damaged (or dry) area of the struck panel was defined as the absence of paint layers, LSP layer and surface resin from CFRP sheets. All panels in figure 3 exhibited structural damage to only 0-1 CFRP sheet.
权利要求:
Claims (12) [1] 1. Method for protecting a substrate against lightning CHARACTERIZED by the fact that it comprises: (i) providing a substrate, (ii) providing a lightning protective composition to the substrate, wherein the lightning protective composition comprises a curable, charged material capable of self-assembly to form conductive strokes during a curing process, in which the material curable comprises a curable organic compound and a charge, said organic compound comprising a relatively non-polar resin and a polar curing agent and said charge being comprised of particles, said particles being coated with a non-polar coating and comprising a material that is electrically conductor and said coated charge particles being mixed into said organic compound, and (iii) curing the composition by means of a heat application, wherein the curing agent reacts with the curable organic compound resin forming a polymer containing polar portions in this, resulting in a repulsion interaction between the nonpolar coating of the charge and the polar portions in the polymer, providing self-assembly of the charges in conductive courses through the composition. [2] 2. Method according to claim 1, CHARACTERIZED by the fact that the curable organic compound comprises diglycidyl bisphenol F ether, preferably wherein the curable organic compound further comprises a curing agent, preferably wherein the curing agent comprises a polyamine anhydride adduct based on the reaction between phthalic anhydride and diethylenetriamine. [3] 3. Method, according to claim 1, CHARACTERIZED by the fact that the conductivity of the cured self-assembled composition is greater than 100 times Petition 870190126679, of 12/02/2019, p. 55/58 2/3 the conductivity of an unmounted cured composition having an equivalent amount of conductive charge. [4] 4. Method, according to claim 1, CHARACTERIZED by the fact that the charge comprises silver. [5] 5. Method according to claim 1 or 4, CHARACTERIZED by the fact that the coating comprises stearic acid. [6] 6. Method, according to claim 1, CHARACTERIZED by the fact that it also comprises the stage of heating the composition to cure the material. [7] 7. Method, according to claim 1, CHARACTERIZED by the fact that the charge particles are sintered to form self-assembled sintered conductive strokes. [8] 8. Method according to claim 1, CHARACTERIZED by the fact that the lightning protective composition is incorporated into a laminated structure further comprising a prepreg substrate, preferably in which the laminated structure further comprises an additional preformed conductive matrix, preferably wherein the preformed conductive matrix comprises an expanded metal sheet. [9] 9. Method, according to claim 1, CHARACTERIZED by the fact that the self-assembled material also provides a course for the base for at least one electrical device. [10] 10. Method according to claim 1, CHARACTERIZED by the fact that the composition comprises less than 40% by volume of conductive charge, or that the composition comprises less than 15% by volume of conductive charge. [11] 11. Method, according to claim 1, CHARACTERIZED by the fact that the step of providing a lightning protection composition to a Petition 870190126679, of 12/02/2019, p. 56/58 3/3 substrate comprises the following steps: identify a damaged section of a lightning protection system comprising at least one discontinuous conductive course; deposit the composition on the damaged section; and curing the deposited composition to provide at least one self-assembled conductive course by completing at least one discontinuous conductive course in the damaged section. [12] 12. Method according to claim 10, CHARACTERIZED by the fact that the damaged lightning protection system comprises at least one of a conductive expanded metal sheet, metal mesh, carbon-metal fiber, metallized carbon or charged conductive polymer, or in which the damaged lightning protection system comprises a curable material capable of self-assembly to form conductive strokes during a curing process.
类似技术:
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同族专利:
公开号 | 公开日 EP2440623B1|2016-10-05| EP2440623A1|2012-04-18| US20110014356A1|2011-01-20| BR112012000203A2|2016-11-22| US20160362565A1|2016-12-15| JP5744015B2|2015-07-01| EP2440622B1|2016-08-31| CN102803405A|2012-11-28| BRPI1010855A2|2016-04-05| US20170226351A9|2017-08-10| JP2012530359A|2012-11-29| JP2012529978A|2012-11-29| WO2010144770A1|2010-12-16| US20100315105A1|2010-12-16| CN102803405B|2016-06-08| KR20120046164A|2012-05-09| CN102803406A|2012-11-28| CN102803406B|2015-10-14| KR20120037464A|2012-04-19| EP2440622A1|2012-04-18| WO2010144762A1|2010-12-16|
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法律状态:
2018-04-10| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]| 2019-01-29| B06T| Formal requirements before examination [chapter 6.20 patent gazette]| 2019-09-03| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]| 2019-12-31| B09A| Decision: intention to grant [chapter 9.1 patent gazette]| 2020-01-28| 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 11/06/2010, OBSERVADAS AS CONDICOES LEGAIS. |
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申请号 | 申请日 | 专利标题 US18649209P| true| 2009-06-12|2009-06-12| US18641509P| true| 2009-06-12|2009-06-12| PCT/US2010/038250|WO2010144762A1|2009-06-12|2010-06-11|Method for protecting a substrate from lightning strikes| 相关专利
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