CURABLE COMPOSITE MATERIAL, AND, METHODS FOR MAKING A CURABLE COMPOSITE MATERIAL AND FOR MAKING A CO

专利摘要:
curable composite material, and, methods for making a curable composite material and for making a composite structure. it is a curable composite material that can be used in applications where both high mechanical performance and high electrical conductivity are required. the curable composite material includes two or more layers of reinforcing fibers that have been infused or impregnated with a curable matrix resin and an interlaminar region that contains carbon nanomaterials, e.g., carbon nanotubes, and hardening insoluble polymer particles. carbon nanomaterials are significantly smaller in size compared to polymeric hardening particles. polymeric hardening particles are substantially insoluble in the matrix resin upon curing of the composite material and remain as discrete particles in the interlaminar region after curing. methods for making curable composite materials and cured composite structures are also disclosed.
公开号:BR112016013450B1
申请号:R112016013450-8
申请日:2014-12-05
公开日:2021-08-24
发明作者:Carmelo Luca Restuccia；Fiorenzo Lenzi；Emiliano Frulloni
申请人:Cytec Industries Inc；
IPC主号:

专利说明:

BACKGROUND
[001] In the aerospace industry, the use of fiber-reinforced polymer composites in aircraft primary and secondary structures is becoming more prevalent. Composite structures are traditionally produced by laminating multiple layers (or folds) of resin-impregnated fibrous reinforcements (known as pre-impregnated) onto a mold surface, followed by consolidation and/or curing. The advantages of fiber reinforced polymer composites include high strength to weight ratio, excellent wear resistance, corrosion resistance and flexibility, allowing for a significant reduction in component parts and reducing the need for fasteners and gaskets. However, the application of these materials to primary and secondary structures of modern aircraft presents special obstacles due to the dielectric nature of the matrix resin. Although the use of carbon fibers as reinforcing fibers in composite materials can provide some degree of electrical conductivity along their longitudinal direction due to their graphitic nature, the dielectric properties of matrix resins in composite materials reduce the overall electrical conductivity of the materials. composites.
[002] Increasing the electrical conductivity of fiber-reinforced polymer composites is desirable in order to meet the requirements for lightning protection of an aircraft and to avoid a phenomenon called "edge glare", which is particularly critical for wing assembly composite. The edge glow phenomenon manifests as an intense glow or spark in the composite skin/stringer assembly with enough energy to be a potential ignition source of fuel vapors.
[003] This edge glow phenomenon can appear during a lightning strike event, especially in composite laminates that have low electrical conductivity in the z direction. During a lightning strike event, a transient load with high current travels through the skin and then enters the wing substructure (eg, spar or structural ribs) due to fasteners connecting the two composite parts. So typically, in a composite skin/stringer assembly, the current runs partially through the skin and partially through the stringer representing one of the walls of the fuel tank.
[004] The current passes laterally from the fasteners through the adjacent composite folds of the stringer and tends to travel along the fibers due to the higher electrical conductivity compared to the resin matrix. This path can generate the typical intense glow or sparks on the edge of the stringer/rib cap, which is called the “edge glow” phenomenon by those skilled in the art.
[005] Figure 1 shows a potential critical current path during a lightning strike event in a composite wing box. The edge glow phenomenon seems more critical when the resin between the fiber reinforcement plies is highly resistive and, consequently, current tends not to flow between the plies. If the conductivity in the z-direction is too low, significant voltage drops can be produced between bends during lightning strike, thus increasing the risk of edge glare.
[006] As known to those skilled in the art, the edge glow phenomenon is associated with surface electron ejections or plasma generation at the composite edges and often appears as a type of resin explosion. Uncertainty regarding the nature of this phenomenon imposed several precautions regarding the ignition capabilities of fuel vapors during a lightning strike event.
[007] A conventional solution is to apply a seal to the fuel tank (see Figure 2). An example of such a fuel tank seal is the LE JOINT FRANCAIS PR 1776 Class B seal. However, such a method carries additional weight and is not always effective due to lack of standardization and difficulties in sealant application. Over time, the seal becomes ineffective due to aging or can be completely removed by the fuel in the tank. Additionally, a lightning strike can result in the generation of high pressure gases at the cutting edge that can shatter the edge seal. There remains a need for a multifunctional composite material that addresses the edge gloss problem discussed above while providing good mechanical properties such as impact strength and delamination. SUMMARY
[008] In this document, composite materials with electrical conductivity and impact resistance properties are disclosed. These composite materials contain polymeric stiffening particles and nanosized carbon-based structures in the interlaminar region between adjacent layers of reinforcing fibers. The polymeric hardening particles are substantially insoluble in the thermosetting matrix resin in the interlaminar region during the curing of the composite materials and remain as discrete particles in the interlaminar region of the cured composite materials. BRIEF DESCRIPTION OF THE DRAWINGS
[009] Figure 1 shows the typical current path during a lightning strike event in a composite wing box that generates the phenomenon of "edge glow".
[010] Figure 2 shows a sealant applied to the wing cap edge of the typical construction of a composite wing.
[011] Figure 3 schematically illustrates a curable composite material with interlaminar regions that contain hardening particles and carbon nanomaterials, according to an embodiment of the present disclosure.
[012] Figure 4 schematically illustrates a curable composite material with interlaminar regions that contain hardening particles and carbon nanomaterials uniformly dispersed in the matrix, according to another embodiment of the present disclosure.
[013] Figure 5 and Figure 6 illustrate a method to manufacture a composite material according to a modality.
[014] Figure 7 and Figure 8 illustrate a method for manufacturing a composite material according to another embodiment of the present disclosure.
[015] Figures 9A and 9B show the mechanical properties of a composite laminate modified with carbon nanotubes (CNTs) versus those of an unmodified composite laminate.
[016] Figures 10A and 10B show the effect of different polymeric hardening particles on the mechanical properties of composite materials modified with CNT.
[017] Figure 11 shows a micrograph image of the cross section of a cured laminate (4b) that contains CNTs and polyphthalamide particles.
[018] Figure 12 shows a micrograph image of the cross section of a cured laminate (4a) that contains CNTs and aromatic polyimide particles.
[019] Figure 13 shows the effect of different polymeric hardening particles on the z-direction CC conductivity of composite laminates modified with CNT and those not modified with CNTs. DETAILED DESCRIPTION
[020] It is widely accepted in the aerospace industry that two of the main design requirements for composite aircraft structures are their resistance to specific impact events and their tolerance to catastrophic failures caused by propagation of damage after impact.
[021] The interlaminar region of a composite laminate presents one of the most challenging failure mechanisms to treat. Delamination of such a composite laminate is an important failure mode for composite materials. Delamination occurs when two laminated layers separate from each other. Important design limiting factors include energy required to initiate delamination and energy required to propagate it.
[022] The need to improve the impact strength performance of composite structures, especially for primary aircraft structures, has triggered the development of a new generation of composite materials hardened with interlaminar particles. Such a technological solution provides high impact resistance to carbon fiber reinforced composites, but also creates an interlaminar region of electrical insulation between adjacent bends, resulting in a significant reduction in the electrical conductivity of the overall composite structure especially in the z direction. The “z direction” refers to the direction orthogonal to the plane in which the reinforcing fibers are disposed in a composite structure or the geometric axis through the thickness of the composite structure.
[023] The electrical conductivity of composite materials can be improved by incorporating different conductive materials, such as conductive particles, in the fiber-reinforced polymer composite matrix resin, or in the interlaminar regions of a composite structure with multiple layers, for example, lamination of prepreg. For example, metallic fillers can be added at high loads to increase the electrical conductivity of the resin, but this leads to significant weight gain and reduction in impact-related properties such as Compressive Strength After Impact (CAI) and toughness of the fracture in mode I and II (GIc and GIIc). As such, prior art solutions are such that the z-direction conductivity of a composite can be improved, but not, simultaneously, its mechanical performance. A cured composite (eg prepreg lamination) with improved impact performance is one with improved CAI and fracture toughness (GIc and GIIc). CAI measures the ability of a composite material to tolerate damage. In the test to measure CAI, the cured composite is subjected to an impact of a given energy and then loaded in compression. The area of damage and depth of notch are measured after impact and before the compression test. During this test, the composite material is constricted to ensure that no elastic instability is occurring, and the strength of the composite material is recorded.
[024] Fracture toughness is a property that describes the ability of a material that contains a crack to resist fracture and is one of the most important properties of a material for aerospace applications. Fracture toughness is a quantitative way of expressing a material's brittle fracture resistance when a crack is present.
[025] Fracture strength can be quantified as rate of deformation energy release (Gc), which is the energy dissipated during fracture per unit of newly created fracture surface area. Gc includes GIC (Mode 1 - opening mode) or Gnc (Mode II - plane shear). The subscript "Ic" denotes Mode I crack opening, which is formed under a normal tensile stress perpendicular to the crack, and the subscript "IIc" denotes Mode II crack produced by a shear stress produced by a shear stress that acts parallel to the plane of the crack and perpendicular to the front of the crack. The initiation and growth of a delamination is often determined by examining the Mode I and Mode II fracture toughness.
[026] It has been revealed that the combination of carbon nanomaterials and certain polymeric particles in the interlaminar region of a multilayer composite material produces a synergistic effect that includes an improvement in conductivity in the z direction and, simultaneously, an improvement in CAI and GIc. The synergistic effect was found by combining the positive effects of carbon nanomaterials with the positive effects of hardening particles, so the interaction of these components in the composite material produces an effect greater than the sum of their individual effects.
[027] It is disclosed in this document a multifunctional and curable composite material, which can be used successfully in those aircraft applications where high mechanical performance and high electrical conductivity are required. In the cured state, the improved electrical conductivity of the composite material can function to diffuse or dissipate electrical currents, such as those generated by a lightning strike, over a larger area of a composite structure produced from the composite material, thereby reducing the probability of catastrophic damage to localized portions of the composite structure. As such, using this multifunctional composite material can be an effective solution to mitigate the direct effect of lightning strike and to prevent the edge shine phenomenon in the composites discussed above. In addition, the cured composite material provides the added benefit of electromagnetic shielding.
[028] One aspect of the present disclosure is directed to a curable composite material composed of two or more layers of reinforcing fibers that have been infused or impregnated with a curable matrix resin, preferably a thermosetting resin. The interlaminar region between adjacent layers of reinforcing fibers contains a curable matrix resin with carbon nanomaterials dispersed throughout and polymeric stiffening particles incorporated in the same matrix resin. Carbon nanomaterials are significantly smaller in size compared to polymeric hardening particles. The polymeric hardening particles are substantially insoluble in the matrix resin upon curing of the composite material and remain as discrete particles in the interlaminar region after curing. In certain embodiments, the polymeric hardening particles are expandable particles. It is preferred that the interlaminar region is free of any soluble thermoplastic particles that dissolve in the matrix resin upon curing.
[029] The resin in the interlaminar region (without nanomaterials and hardening particles) can be the same or different in relation to the matrix resin that impregnates the reinforcing fibers. In some embodiments, the matrix resin that impregnates the reinforcing fibers also contains carbon nanomaterials dispersed therein.
[030] Figure 3 schematically illustrates a curable composite material 20 according to an embodiment of the present disclosure. The composite material 20 contains interlaminar regions 20a and 20b formed between layers 21, 22, 23 of reinforcing fibers that have been infused or impregnated with a curable matrix resin. Each of the interlaminar regions 20a and 20b contains a curable matrix resin (24a, 24b, respectively) with carbon 25 nanomaterials dispersed therein and polymeric hardening particles 26 incorporated in the same matrix resin. The resin composition (without nanomaterials and hardening particles) of the interlaminar resin 24a and 24b can be the same or different from that of the matrix resin that impregnates the fiber layers 21, 22, 23. When the interlaminar resin (24a, 24b) ) is similar to that of the matrix resin impregnating the fiber layers 21, 22, 23, the resin matrices contain one or more thermosetting resins in common. The polymeric hardening particles 26 can be positioned side by side and together form a single layer of particles. In this way, the depth of the interlaminar region is determined by particle sizes. Preferably, the hardening particles 26 are similar in size (e.g., spherical particles having approximately the same diameter), and the depth of the interlaminar region is approximately equal to or slightly greater than the average diameter of the hardening particles 26.
[031] Figure 4 schematically illustrates a curable composite material 40 according to another embodiment of the present disclosure. The composite material 40 contains the interlaminar regions 40a and 40b formed between layers 41, 42, 43 of reinforcing fibers, and the interlaminar regions contain polymeric stiffening particles 46. The reinforcing fibers (41, 42, 43) and polymeric particles 46 are infused with or embedded within a curable matrix resin which contains 45 carbon nanomaterials dispersed therein. As in the embodiment shown in Figure 3, the polymer particles 46 can be positioned side by side and together form a single layer of particles. Furthermore, the depth of the interlaminar region can be determined by particle sizes. Preferably, the hardening particles 46 are similar in size (e.g., spherical particles having approximately the same diameter), and the depth of the interlaminar region is approximately equal to or slightly greater than the average diameter of the hardening particles 46.
[032] Upon curing, composite materials cured, according to the modalities disclosed in this document, have the following properties: electrical conductivity in the z direction greater than 1 S/m (siemens per meter) as measured under DC conditions according to a 4-probe test method, CAI after impact at 30 J greater than 250 MPa as measured in accordance with ASTM7136/37 and mode I interlaminar fracture resistance (GIc) greater than 300 J/m2 as measured in accordance with the EN6033 standard. CARBON NANOMATERIALS
[033] The term "carbon nanomaterials" or nanosized carbon-based structures, as used herein, refers to materials that have at least one dimension less than about 0.1 micrometer (<100 nanometers) and composite entirely or mainly by carbon atoms arranged, on the molecular scale, in pentagons or hexagons, or both.
[034] Nanosized carbon structures can have an aspect ratio of 50:1 to 5,000:1. The term "aspect ratio" as used herein refers to the ratio of the longest dimension to the shortest dimension of a three-dimensional body. This term is applicable to structures of any shape and size. When this term is used in relation to spherical or substantially spherical particles, the relevant ratio could be that between the largest cross-sectional diameter and the smallest cross-sectional diameter of the spherical body. As an example, a perfectly spherical particle could have an aspect ratio of 1:1.
[035] The nanosized carbon structures for the purpose intended in this document include, but are not limited to, carbon nanotubes, carbon nanofibers, carbon nanocords, carbon nanoties, carbon nanofibrils, carbon nanoneedles, carbon nanosheets, nano -carbon rods, carbon nanocones, carbon nanorolls (roll-like shapes) and carbon nano-ohms, carbon black, graphite nanoplates or nanodots, graphenes and other types of fullerene materials. Any of these fullerene materials can have a partial or full metallic coating. The nanoparticles can be of any suitable three-dimensional shapes, including, for example, spherical, ellipsoidal, spheroid, discoidal, dendritic, rods, disks, cuboid or polyhedral.
[036] The preferred carbon nanomaterials are carbon nanotubes (CNTs). Typically, CNTs are tubular, filament-like structures that have outside diameters in the range of 0.4 nm to about 100 nm, preferably the outside diameter is less than 50 nm and most preferably less than 25 nm.
[037] The CNTs can be of any chirality. Armchair type nanotubes are contemplated. Furthermore, CNTs can be semiconductor nanotubes or any other type that exhibit electrical conductivity. Suitable CNTs can include single-walled carbon nanotubes (SWCNTs), double-walled carbon nanotubes (DWCNTs) and multi-walled carbon nanotubes (MWCNTs). Preferred carbon nanomaterials are MWCNTs.
[038] Carbon nanomaterials for the purposes intended herein may be present in the range of 0.1% by weight to 10% by weight of the total resin content in the composite material, preferably between 0.5% by weight to 2% by weight and more preferably in the range of 1% by weight to 1.5% by weight. As used herein, "% by weight" refers to percent by weight. POLYMER HARDENING PARTICLES
[039] Polymeric hardening particles that are suitable for the purposes herein include thermoplastic or elastomeric particles. As discussed above, suitable hardening particles are particles that are substantially insoluble in the thermosetting matrix resin of the composite materials during the curing thereof and remain as discrete particles in the cured matrix resin after curing. In certain embodiments, the polymeric hardening particles are also expandable particles in the thermosetting matrix resin of the composite material during curing. Furthermore, polymeric hardening particles do not have a non-polymeric coating, such as metal.
[040] It is preferred that the hardening particles are evenly dispersed in the interlaminar region formed between adjacent layers of reinforcing fibers at a content of 2% to 20% based on the weight of the total matrix resin contained in the composite material, preferably within in the range of 5% to 15% and more preferably within the range of 5% to 12%.
[041] The polymeric hardening particles can be of any three-dimensional shape, however, it is preferred that they are substantially spherical. It is also preferred that the hardening particles have an aspect ratio of less than 5:1, preferably the aspect ratio is about 1:1. In reference to hardening particles, the term "aspect ratio" refers to the ratio of the largest cross-sectional dimension to the smallest cross-sectional dimension of the particle.
[042] For spherical particles (approx. 1:1 aspect ratio), the average particle size refers to its diameter. For non-spherical particles, mean particle size refers to the largest cross-sectional dimension of the particles.
[043] For the purposes disclosed herein, polymeric hardening particles may have an average particle size (d50) less than 100 µm, preferably within the range of 50 µm to 90 µm, more preferably 10 µm to 40 µm, as measured by a laser diffraction technique, for example using a MalvernMastersizer 2000 operating in the range of 0.002 nanometer to 2000 micron.
[044] “d50” represents the median of the particle size distribution or, alternatively, is the value in the distribution such that 50% of the particles have a particle size of this value or smaller.
[045] In addition, polymeric hardening particles are larger in size compared to carbon nanostructures. It is preferred that the average particle size (d50) of the polymeric hardening particles is at least 100 times larger than the smallest dimension of the carbon nanostructure.
[046] As an example, when the carbon nanostructures are carbon nanotubes, the average particle size (d50) of the hardening particle is at least 100 times larger than the diameter of the carbon nanotubes.
[047] Determining whether certain particles are insoluble or soluble refers to the solubility of the particles in a particular resin system in which they reside. The resin system can include one or more thermosetting resins, curing agents and/or catalysts and mirrored amounts of optional additives to modify the properties of the uncured or cured matrix resin.
[048] Hot stage microscopy can be used to determine whether a particle is insoluble, partially soluble, or expandable in a resin system. First, a sample of dry polymeric particles (which are not combined with a resin) is characterized by microscopy, and the images analyzed using ImageJ software from the NationalInstitutesof Health (Bethesda, Maryland, USA) to determine the mean size of particle and volume. Second, a sample of particles is dispersed into the desired matrix resin through mechanical mixing. Third, a sample of the resulting mixture is placed on a microscope slide, which is then placed in a hot stage setup under a microscope. The sample is then heated to the desired cure temperature at the desired ramp rate, and any change in particle size, volume, or shape is continuously recorded at 10 frames per second. Diameter is typically measured for spherical particles while the longer side is measured for non-spherical ones to determine changes in size and volume using ImageJ software. All hot stage testing can be performed at a 10 wt% particle loading on a matrix resin that does not contain a curative or catalyst.
[049] When hardening particles are subjected to hot stage microscopy analysis above, and the change in particle diameter or volume is zero or less than 5% compared to the original "dry" particles, then the particle is considered as being insoluble and not intumescent. When the hardening particle is subjected to the above hot stage microscopy analysis and there is an increase in particle diameter or volume by more than 5%, then the particle is considered to be “swellable” as well as insoluble. The swelling is caused by the infusion of the surrounding resin on the outer surface of the particle.
[050] In some embodiments, insoluble particles include particles that fuse during analysis by hot stage microscopy, but are incompatible with the matrix resin and therefore reform into discrete particles upon cooling. For analytical purposes only, insoluble particles may flow during analysis by hot stage microscopy, and the degree of crystallinity may also change.
[051] In cases where diameter or volume may be difficult to determine, an alternative analysis can be used. A 16 ply quasi isotropic composite panel produced from unidirectional prepreg tapes and containing a 10% particle loading based on the weight of the total matrix resin in the resin-rich interlaminar regions can be fabricated according to a schedule of curing and then the cured panel is cut in the cross-sectional direction for evaluation by microscopy. If the particles remain as discernible and discrete particles after curing, then the particles are considered to be insoluble particles. If the particles completely dissolve in both the interlaminar region and the matrix surrounding the fiber bed and are not discernible as discrete particles upon cooling, then the particles are not considered to be insoluble interlaminar particles.
[052] For epoxy-based matrix resin, the composition of insoluble polymeric particles may contain at least one polymer selected from: polyamideimide (PAl), aliphatic polyamides (PA), polyphthalamide (PPA), polyaryletherketones (PAEK), such as polyetheretherketone (PEEK) and polyetherketone ketone (PEKK), polyphenylene sulfide (PPS), liquid crystal copolymers (LCPs), copolymers thereof and derivatives thereof. In some embodiments, the polymer particle composition contains at least one elastomeric polymer or material selected from: cross-linked polybutadiene, polyacrylic, polyacrylonitrile, polystyrene, copolymers thereof, and derivatives thereof (such as DuoMod DP5045 sold from ZeonChemicalsInc).
[053] In preferred embodiments, the insoluble particles are insoluble thermoplastic particles that do not dissolve during the curing process and remain within the interlaminar regions of the cured composite material. Examples of suitable insoluble thermoplastic particles include polyamideimide (PAl) particles and polyamide (PA) particles (eg, nylon) or polyphthalamide (PPA) particles, which are insoluble in an epoxy resin system during the curing cycle thereof. .
[054] Certain grades of polyimide particles may be suitable as insoluble hardening particles. For example, polyimides prepared from benzophenatetracarboxylic acid dianhydride (BTDA), 4,4'-methylenedianiline (MDA) and 2,4-toluenediamine (TDA), and which have a non-phthalimide carbon content containing between 90 and 92 percent aromatic carbons.
[055] Insoluble thermoplastic particles have been shown to be effective as interlaminar hardeners to prevent loss of hot/wet performance. Because these thermoplastic particles remain insoluble in a matrix resin even after curing, they impart improved toughness, damage tolerance, hot/wet performance, processing, microcrack resistance, and reduced solvent sensitivity to the cured resin.
[056] The manufacturing methods of the insoluble particles described herein may include, in any order, emulsification, precipitation, emulsion polymerization, washing, drying, extrusion, lamination, grinding, cryo-crushing, jet laminating and/or sieving the particles. Those skilled in the art will appreciate that these steps can be achieved by any one of a number of methods known in the art.
[057] Insoluble particles used for the purposes intended herein include crosslinked thermoplastic particles. According to one embodiment, the crosslinked thermoplastic particle is composed of a crosslinking network created by reacting one or more crosslinkable thermoplastic polymers that have one or more reactive groups with a crosslinking agent that is chemically reactive to the reactive groups, in which the crosslinking agent directly crosslinks the polymer chains to each other through the reactive groups. Reactive groups can be end groups or pendant groups on the polymer backbone. The direct cross-linking reaction of this modality can be described as "binding" the polymer molecules by direct cross-linking the polymer chains using one or more reactive groups.
[058] The above crosslinked thermoplastic particles can be produced by the process as described in Patent Application Publication No. US 2010/0304118, published December 2, 2010, which is incorporated herein by reference. This method includes dissolving a thermoplastic polymer with reactive functional groups, a crosslinking agent, and a catalyst in a common solvent that is immiscible with water. An emulsion is then created in water using a non-ionic surfactant so that emulsified particles are formed. The emulsified particles are subsequently dried and cured so that the polymer chains become chemically cross-linked. The reaction conditions and the type of crosslinking agent will determine the final properties of the particles. Reaction conditions, such as temperature, result in increased crosslinking. Crosslinking agents with two or more reactive sites (i.e., functional groups) are preferred. The resulting crosslinked thermoplastic particles are discrete, free-moving particles that can be added to a curable resin.
[059] Examples of suitable thermoplastic polymers that bear reactive groups that are susceptible to cross-linking include, but are not limited to, one or more of a polyether, polycarbonate, polyetherimide (PEl), polyamide, polyimide, polysulfone, polyethersulfone (PES) , polyphenylene oxide (PPO), polyetherketones, polyaryletherketones (PAEK), such as polyetheretherketone (PEEK) and polyetherketone ketone (PEKK), polyphenyl sulfides (PPS), polyhydroxyethers, styrene-butadiene, polyacrylates, polyacetol, polybutyleneterephthalate imide, polyetherethersulfone (PEES), blends thereof, or a copolymer thereof, PES homopolymers (such as SUMIKAEXCEL 5003P from Sumitomo ChemicalCo. or Radel® PES from Solvay), or PEES homopolymers. Specific examples of PES copolymers include PES/PEES copolymer with various repeat unit ratios. The thermoplastics listed above can be used as a single component to form a particle or, when more than one thermoplastic polymer is used, a hybrid structure or a hybrid particle is formed.
[060] In other embodiments, the crosslinked particles are formed from a mixture of thermoplastic polymers. In still other embodiments, the crosslinked particles described herein can be formed from a hybrid structure in which two or more thermoplastic polymers are used.
[061] The reactive groups in crosslinkable thermoplastic polymers can be one or more of the following: amine; hydroxyl; anhydrous; glycidyl; carboxylic acid; maleimide; isocyanate; phenolic; nadimide; cyanate ester; acetylene; vinyl; vinyl ester; diene; or derivatives thereof. In some cases, polymer chain installations can serve as crosslinking points (for acrylic and methacrylic family as well as some unsaturated rubbers, vinyl esters or unsaturated polyesters). The number of reactive groups can be a minimum of one reactive group per chain and, in some embodiments, is considered the lowest fraction necessary to create a connected polymer backbone; a number around or greater than one is preferred to produce a tightly crosslinked polymer or interpenetrating network. Polymers with functionalities greater than 2 will easily produce highly reacted gels.
[062] Depending on the chemical nature of the end groups/functionalities of the thermoplastic polymer, a suitable multifunctional crosslinking agent with multiple reactive sites can be selected. Examples of such crosslinking agents are: alkylated melanin derivatives (eg CYMEL® 303), acid chlorides (eg 1,3,5-benzenetricarbonyl trichloride), multifunctional epoxides (eg ARALDITE® MY0500, MY721), carboxylic acids (eg benzenetetracarboxylic acid).
[063] In another embodiment, the crosslinked particle is composed of a polymer network (IPN), which is composed of thermoplastic polymer chains intertwined with an independent crosslinking network. IPN is created by reacting one or more compounds (eg, crosslinkable monomers or polymers) that have one or more reactive groups with a crosslinking agent that is chemically reactive to the reactive groups in the presence of a thermoplastic polymer. The reaction (which takes place under certain conditions of crosslinking or curing) causes the compounds to become crosslinked via the reactive groups, thus forming an independent crosslinking network. As such, thermoplastic polymer chains are intertwined with the independent crosslinking network at a molecular level to form an IPN. This approach can be described as “binding” thermoplastic polymer chains through the formation of a separate and independent crosslinking network, thus creating an interpenetrating network. Thus, in this modality, the thermoplastic polymer does not need to have reactive groups in it. Such crosslinked particles can be produced by the process described in Patent Application Publication No. US 2010/0305239, published December 2, 2010, which is incorporated herein by reference. The resulting crosslinked thermoplastic particles are discrete particles that can be added to a curable resin.
[064] As an example, a particle crosslinked with an IPN can be created by: (i) forming an emulsion that contains a thermoplastic polymer, a multifunctional epoxy resin and an amine curing agent with the ability to crosslink the epoxy resin; (ii) removing the solvent from the emulsion and collecting the condensate, which is in the form of solid particles; (iii) drying the particles followed by curing (eg by heating) so that the epoxy resin becomes cross-linked. As a result of curing, the crosslinked epoxy forms an IPN with the thermoplastic polymer in each particle.
[065] Certain thermoplastic crosslinked and intumescent particles are particularly suitable as interlaminar hardening particles. These crosslinked thermoplastic particles become swollen in an epoxy-based resin system during cure, but remain as discrete particles in the cured resin. The swelling is caused by the infusion of the surrounding resin on the outer surface of the particle.
[066] These crosslinked and intumescent thermoplastic particles also form a “gradient interface” with the surrounding matrix resin in which they reside during cure. The term "gradient interface" as used herein refers to the gradual and strong interface between each of the particles and the surrounding matrix resin. A gradient interface is achieved using modified crosslinked thermoplastic particles that are thermodynamically compatible with the thermosetting resin, eg epoxy. The concentration of thermoplastic polymer in the core of a crosslinked thermoplastic particle is greatest at the center and gradually decreases towards the outer surface of the particle from the outer surface and moves towards the core. This gradual decrease in thermoplastic concentration from the core to the outer surface of the thermoplastic particle forms the gradient interface between each of the thermoplastic particles and the surrounding matrix resin. Thus, there is no sharp delineation or transition between the thermosetting resin and the thermoplastic particle. If a sharp delineation or transition were present, the interface between the thermoset and thermoplastic resin could be much weaker in a composite material compared to a composite material that contains a gradient interface. As such, these crosslinked thermoplastic particles are considered "intumescent" due to the fact that the resin, which surrounds the particle, diffuses into the particles across the outer surface of the particle when the resin is heated and its viscosity is reduced, thus resulting in an increase in particle size. However, the crosslinked particles will remain as discrete and discernible particles after resin cures.
[067] The crosslinked thermoplastic particles described herein are discrete, free-moving (i.e., split-state) particles that can be added to a thermosetting resin, such as an epoxy-based resin and are chemically crosslinked to prevent its complete dissolution in the resin during the resin curing cycle. Furthermore, they are designed to be thermodynamically compatible with the thermosetting resin.
[068] "Discrete particle", as used herein, refers to a particle that is discernible in a matrix resin and that can be detected using Scanning Electron Microscopy (SEM), Optical Microscopy or Microscopy of Differential Interference Contrast (DIC). MATRIX RESIN
[069] The curable matrix resin (or resin composition) to impregnate/infuse the reinforcing fibers is preferably a hardenable or thermosetable resin that contains one or more uncured thermoset resins, which include, but are not limited to, resins epoxy, imides (such as polyimide or bismaleimide), vinyl ester resins, cyanate ester resins, isocyanate modified epoxy resins, phenolic resins, furan resins, benzoxazines, formaldehyde condensate resins (such as with urea, melamine or phenol), polyesters, acrylics, hybrids, blends and combinations thereof.
[070] Suitable epoxy resins include aromatic diamine polyglycidylade derivatives, aromatic monoprimary amines, aminophenols, polyhydric phenols, polyhydric alcohols, 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 novolacs based on cresol and phenol.
[071] Specific examples are 4,4'-diaminodiphenylmethane tetraglycidyl derivatives (TGDDM), resorcinoldiglycidyl ether, triglycidyl-p-aminophenol, triglycidyl-m-aminophenol, bromobisphenol F diglycidyl ether, tetraglycidyl derivatives of diaminodiphenylmethane, triglycidyl ether - hydroxyphenyl methane, polyglycidyl ether of phenol-formaldehyde novolac, polyglycidyl ether of o-cresol novolac or tetraglycidyl ether of tetraphenylethane.
[072] Commercially available epoxy resins suitable for use in the host matrix resin include N,N,N',N'-tetraglycidyldiaminodiphenylmethane (e.g. MY 9663, MY 720 and MY 721 by Huntsman); N,N,N',N'-tetraglycidyl-bis(4-aminophenyl)-1,4-diisopropylbenzene (e.g. EPON 1071 from Momentive); N,N,N',N'-tetraclicidyl-bis(4-amino-3,5-dimethylphenyl)-1,4-diisopropylbenzene, (for example EPON 1072 from Momentive); p-aminophenol triglycidyl ethers (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 to 20 Pa 2 at 25°C glycidyl ethers of phenol Novolac resins (eg DEN 431 or DEN 438 from Dow) phenolic novolac based on dicyclopentadiene (eg Tactix 556 from Huntsman); diglycidyl ,2-phthalate (eg GLY CEL A-100) diglycidyl derivative of dihydroxydiphenyl methane (Bisphenol F) (eg PY 306 from Huntsman) Other epoxy resins include cycloaliphatic such as 3-carboxylate ',4'-epoxycyclohexyl-3,4-epoxycyclohexane (eg CY 179 from Huntsman).
[073] In general, the curable matrix resin contains one or more thermosetting resins in combination with other additives, such as curing agents, curing catalysts, comonomers, rheology control agents, tackifiers, inorganic or organic fillers, thermoplastic and/or elastomeric polymers as hardening agents, stabilizers, inhibitors, pigments, dyes, flame retardants, reactive diluents and other additives well known to those skilled in the art to modify the properties of the matrix resin before and after curing.
[074] Suitable hardening agents for curable resin composition include, but are not limited to, homopolymers or copolymers, alone or in combination with polyamides, copolyamides, polyimides, aramids, polyketones, polyetherimides (PEI), polyetherketones (PEK) , polyetherketone (PEKK), polyetherketone (PEEK), polyethersulfone (PES), polyetherethersulfone (PEES), polyesters, polyurethanes, polysulfones, polysulfides, polyphenylene oxide (PPO) and modified PPO, poly(ethylene oxide) (PEO) and oxide of polypropylene, polystyrenes, polybutadienes, polyacrylates, polymethacrylates, polyacrylics, polyphenylsulfone, high performance hydrocarbon polymers, liquid crystal polymers, elastomers and segmented elastomers.
[075] The addition of curing agent(s) and/or catalyst(s) to the curable matrix resin is optional, but their use may increase cure rate and/or reduce cure 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 particularly preferably are diaminodiphenylsulfones, for example in cases where the amino groups are in the meta or para 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 TM) and dicyandiamide (eg AMICURE TM CG 1200 from Pacific AnchorChemical).
[076] Suitable curing agents also include anhydrides, particularly polycarboxylic anhydrides, such as nadic anhydride, methylnadic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylene tetrahydrophthalic anhydride, and trihydrophthalic anhydride.
[077] The curable matrix resin in the interlaminar region is also a hardenable or thermosetting resin that contains one or more uncured thermosetting resins of the type discussed above. In certain embodiments, the curable matrix resin in the interlaminar region is the same as the matrix resin in the region containing the reinforcing fibers. In other embodiments, the resin in the interlaminar region is different from the matrix resin in the region containing the reinforcing fibers. REINFORCEMENT FIBERS
[078] For manufacturing high-performance composites and prepregs, suitable reinforcing fibers are, however, without limitation, fibers that have a high tensile strength, preferably greater than 3,447 MPa (or 500 ksi). Fibers that are useful for this purpose include carbon or graphite fibers, glass fibers and fibers formed from silicon carbide, alumina, boron, quartz 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 DuPontCompany under the trade name KEVLAR. The reinforcing fibers can be used in the form of discontinuous or continuous tows made up of multiple filaments, as continuous unidirectional or multidirectional tapes, or as woven, non-crimped or non-woven fabrics. The woven shape can be selected from plain weave, satin or twill style. The uncurled cloth can have a variety of pleats and fiber orientations.
[079] Fibers can be sized or not sized. Fibers can typically be added at a concentration of 5 to 35, preferably at least 20% by weight. For structural applications it is preferred to use continuous fiber, eg glass and carbon, especially at 30 to 70, more especially 50 to 70% by volume. MANUFACTURING OF PRE-IMPREGNED COMPOUNDS AND LAMINATES
[080] According to an embodiment, specific amounts of carbon nanomaterials and polymeric hardening particles are mixed with a curable resin composition prior to impregnation of reinforcing fibers (ie, prior to prepreg fabrication). In this embodiment, a resin film is manufactured by first coating the particle-containing resin composition onto a release paper. Then, one or two such resin film is/are laminated onto one or both sides of a layer of reinforcing fibers under the aid of heat and pressure to impregnate the fibers, thus forming a layer of reinforced polymer. fiber (or prepreg ply) with specific fiber weight by area and resin content. During the lamination process, the hardening particles are removed by filtration and remain external to the fiber layer due to the fact that the particle size is greater than the spacing between the fiber filaments. The resulting prepreg ply contains a structural fiber reinforced layer adjacent to one or two layers of matrix resin in which the polymeric hardening particles are incorporated. Subsequently, when two or more plies of prepreg which contain stiffening particles therein are laminated onto each other by means of a lamination process, the stiffening particles are positioned in the interlaminar region between two adjacent fiber layers. In this embodiment, the matrix resin in the interlaminar region (without polymeric hardening particles) is the same as the matrix resin contained in the structural fiber reinforced layer and contains uniformly dispersed carbon nanomaterials.
[081] In a second embodiment, a curable matrix resin without carbon nanomaterials or polymeric hardening particles is coated onto a release paper to form a resin film. This resin film is then placed in contact with one side of a fiber layer. Upon application of pressure, the resin film impregnates the fibers and leaves little or no resin on the outer surfaces of the fiber layer. Subsequently, a curable resin film containing carbon nanomaterials and polymeric hardening particles is laminated onto an exposed outer surface of the resin-impregnated fiber layer. The curable resin that carries the polymeric stiffening nanomaterials and particles can be the same or different from the matrix resin that impregnates the reinforcing fibers. As a result, the particle-containing resin layer remains outside the impregnated fiber layer and no longer impregnates the fibers. A plurality of structures are laminated together to form a composite structure with carbon nanomaterials and polymeric stiffening particles positioned in the interlaminar regions.
[082] In a third embodiment, a curable matrix resin containing carbon nanomaterials but not polymeric hardening particles is coated onto a release paper to form a resin film. This resin film is then placed in contact with one side of a fiber layer. Upon application of pressure, the resin film impregnates the fibers and leaves little or no resin on the outer surfaces of the fiber layer. Subsequently, a curable matrix resin film containing carbon nanomaterials and polymeric hardening particles is laminated to an exposed outer surface of the resin-impregnated fiber layer. When a plurality of such structures are laminated together to form a composite structure, the carbon nanomaterials are uniformly dispersed in the layer containing the reinforcing fibers and in the interlaminar regions containing the interlaminar stiffening particles.
[083] In another embodiment, as illustrated by Figure 5, two films 31, 32 of curable matrix resin without carbon nanomaterials or hardening interlaminar particles are laminated on two opposing surfaces of a layer of fiber 33. The resin films 31, 32 impregnate the fibers and leave little or no resin on the outer surfaces of the fiber layer, resulting in the resin impregnated fiber layer 34. Subsequently, two curable matrix resin films 35, 36 containing carbon nanomaterials and polymeric hardening particles are contacted with opposing surfaces of the resin-impregnated fiber layer 34, as illustrated in Figure 6, to form a sandwich structure. Such an approach tends to produce a well-defined and regular interlaminar region in the cured laminate.
[084] In another embodiment, as illustrated by Figure 7, the two films 51, 52 of curable matrix resin containing carbon nanomaterials but not polymeric hardening particles, are laminated onto two opposing surfaces of a fiber layer 53. The films of resin 51, 52 impregnate the fibers and leave little or no resin on the outer surfaces of the fiber layer, resulting in a fiber layer impregnated with resin 54. Subsequently, two curable matrix resin films 55 and 56 containing carbon nanomaterials and particles polymeric hardeners are contacted with opposing surfaces of the resin-impregnated fiber layer 54, as illustrated in Figure 8, to form a sandwich structure. Such an approach tends to provide a well-ordered laminate and carbon nanotubes evenly dispersed in the laminate.
[085] The term "prepreg" as used herein refers to a sheet or layer of fibers that has been impregnated with a curable resin composition within at least a portion of the fibrous bulk. The prepreg used to make aerospace structures is usually a resin-impregnated sheet of unidirectional reinforcing fibers, eg carbon fibers, which is often called "tape" or "unidirectional tape". Prepregs can be prepregs, fully impregnated or partially impregnated prepregs. The matrix resin impregnating the reinforcing fibers can be in a partially cured or uncured state.
[086] Typically, the prepreg is in a bendable or flexible form that is ready for lamination and molding in a three-dimensional configuration, followed by curing into a final composite part/structure. This type of prepreg is particularly suitable for manufacturing load-bearing structural parts, such as aircraft wings, fuselages, bulkheads and control surfaces. The important properties of cured prepregs are high strength and stiffness with reduced weight.
[087] To form a composite structure, a plurality of prepreg plies can be laminated onto one tool in a stacking sequence to form a "prepreg lamination". The prepreg bends within the lamination can be positioned in a selected orientation relative to each other, eg 0°, ± 45°, 90°, etc. Prepreg laminations can be manufactured by techniques which may include, but are not limited to, manual lamination, automated tape lamination (ATL), advanced fiber positioning (AFP) and filament winding.
[088] The curing of the composite material or prepreg lamination disclosed in this document is generally carried out at elevated temperature up to 200 °C, preferably in the range of 170 °C to 190 °C, and with the use of high pressure to restrict the effects of exhaust gas deformation, or restrict the formation of void space, suitably at pressure up to 1 MPa (10 bar), preferably in the range of 0.3 MPa (3 bar) to 0.7 MPa (7 bar). Preferably, the curing temperature is reached by heating up to 5 °C/min, for example 2 °C/min to 3 °C/min and is maintained for the required period of up to 9 h, preferably up to 6 h, for example, 2 h 4 h. The use of a catalyst in the matrix resin can allow for even lower curing temperatures. The pressure is completely released, and the temperature is reduced by cooling down to 5 °C/min, eg to 3 °C/min. Post-curing at temperatures in the range of 190 °C to 350 °C and atmospheric pressure can be accomplished using suitable heating rates to improve the glass transition temperature of the matrix resin. APPLICATIONS
[089] The compositions described in this document can be used to fabricate cast or molded structural materials, and are particularly suitable for fabricating impact-resistant or charge-bearing composite structures reinforced with fiber with improved bulk electrical conductivity.
[090] The composite materials disclosed in this document are applicable to the manufacture of components for transportation applications, including aerospace, aeronautical, nautical and land, automotive and rail vehicles. For examples, composite materials can be used to fabricate primary and secondary aircraft structures, ballistic and space structures. Such structural components include composite wing structures. The composite materials disclosed herein also find use in building and construction applications, as well as other commercial applications. Notably, composite materials are particularly suited to the fabrication of load-bearing and impact-resistant structures. MEASUREMENT METHODS
[091] The disclosed compositions were characterized according to the methods described below: VOLUME ELECTRIC CONDUCTIVITY - Z DIRECTION
[092] The electrical conductivity in the direction orthogonal to the surface of the cured composite laminates was measured using a Burster-Resistomat 2316 milliohmmeter that records resistance values as the ratio of applied voltage to current in a bridge method. Kelvin test probes were used to create contact between the two surfaces of the sample. All measurements were carried out in accordance with the RT 4-wire measurement method under standard humidity conditions.
[093] Measurements were performed on coupons extracted from defect-free quasi-isotropic panels prepared in accordance with method B of the EN 2565 standard. Square samples approximately 3 mm thick were characterized.
[094] The composite specimen surfaces were prepared by removing the top resin-rich layer to expose the underlying carbon fibers that ensure direct contact with the electrode. Then a commercial silver paste was used to create two electrodes on opposite coupon surfaces.
[095] A minimum of 5 samples per material and lamination has been tested.
[096] The DC electrical conductivity was calculated in [S/m] in accordance with the following equation:
where: R is the measured resistance [in Ohm];l is the thickness of the sample [in m];S is the surface area of the sample [in m2] MECHANICAL CHARACTERIZATION
[097] Compression after impact (CAI) after an impact of 30Joules was determined using 24-ply quasi-isotropic laminates. Measurements were performed at room temperature on coupons extracted from defect-free panels prepared in accordance with method B of standard EN 2565 and cured for 2 hours at 180 °C. The specimens were machined, impacted and tested in accordance with ASTM7136/37 standard.
[098] Mode I interlaminar fracture strength was determined using a 16-ply unidirectional laminate cured with a fluoroethylene polymer (FEP) film as a midplane crack initiator. GIc measurements were performed at room temperature according to EN6033 on coupons extracted from defect-free panels.COMPARATIVE EXAMPLE 1EFFECT OF polymeric hardening particles in composite materials
[099] Matrix resins with polymeric hardening particles (1a, 1b, 1c and 1d) and without polymeric hardening particles (Control 1) were prepared according to the formulations shown in Table 1. All amounts are shown in percentage in weight (% by weight/weight) based on the weight of the formulation.

[0100] In Table 1, Araldite® PY 306 is a Bisphenol F triglycidyl ether resin available from Huntsman, Araldite® MY 0510 is a p-aminophenol resin triglycidyl ether resin available from Huntsman, and SUMIKAEXCEL 5003P is a polymer of polyethersulfone available from Sumitomo ChemicalCo. Particle A is an aromatic polyimide with a glass transition temperature of approximately 340 °C and an average particle size of 40 microns, and is sold under the trade name P84 from Evonik. Particle B is a polyphthalamide with a melting point of approximately 250 °C and an average particle size of 35 microns, sold under the trade name Vestamid® TGP3551 from Evonik. Particle C is a crosslinked, expandable PES-PEES particle with an average particle size of 25 microns from Cytec Industries Inc. Particle D is an aliphatic nylon particle with an average particle size of 25 microns supplied by Evonik under trade name of VESTOSINT® Z2649.
[0101] The matrix was prepared by dispersing the 5003P in the epoxy constituents and heating at 125 °C for approximately 1 hour to dissolve the 5003P. The resulting mixture was cooled to 80°C, and then the remaining constituents were added and thoroughly mixed.
[0102] The resin compositions were then used to produce different unidirectional prepregs (UD). Each of the curable resin compositions disclosed in Table 1 was used to make a resin film by coating the resin composition onto a release paper. Then, two such resin films were laminated onto both sides of a continuous layer of unidirectional carbon fibers (IMS65E from TohoTenax, USA) with the aid of heat and pressure to form a UD prepreg. Each resulting prepreg had an average FAW (weight of fiber per area) of 197 gsm and 35% weight/weight resin content based on total prepreg weight. Test composite laminates were prepared from the prepregs in accordance with method EN2565 discussed above. MECHANICAL RESULTS
[0103] The composite test laminates were subjected to mechanical testing, and the results are shown in Table 2. As seen in Table 2, composite laminates cured with interlaminar hardening particles of polyimide, polyphthalamide, crosslinked PES-PEES or polyamide among fiber layers produced an improvement in damage tolerance (CAI at 30 J) and interlaminar fracture toughness (GIc) values compared to Control 2 (baseline with no hardening particles). BASE AND HARDENED WITH PARTICLE
ELECTRICAL RESULTS
[0104] The z-direction volumetric conductivity of the cured composite laminates was also measured, and the results are shown in Table 3.
[0105] Contrary to the mechanical results in Table 2, the inclusion of polymeric interlaminar hardening particles in cured composite laminates produced a drastic reduction in the DC conductivity in the z direction compared to composites without a well-defined interlaminar region (Control 2). This reduction is mainly due to the dielectric nature of the polymeric hardening particles. For example, the addition of Particle C to the baseline system reduced the z-direction conductivity of the 2c cured laminate by almost an order of magnitude compared to the unmodified baseline (Control 2).TABLE 3. ELECTRICAL RESULTS.
EXAMPLE 2 EFFECT OF polymeric hardening particles in composite materials modified with CNT
[0106] The same curable resin compositions disclosed in Table 1 of Example 1 were modified by dispersing between 1.35% and 1.55% by weight of multi-walled carbon nanotubes (MWCNTs) that have carbon purity >98 %, an average diameter of 15 nm and an average length of about 1 mm. Resin compositions modified with MWCNT are shown in Table 4. All amounts are shown in percent by weight (% by weight/weight) based on the weight of the formulation. TABLE 4. RESIN COMPOSITIONS MODIFIED WITH MWCNT

[0107] The curable matrix resins were prepared based on the formulations in Table 4. The matrix resins were then used to produce UD carbon fiber reinforced prepregs in accordance with the same manufacturing method described in Example 1 Each prepreg had an average FAW of 197 gsm and 35% wt/weight resin content based on total prepreg weight. Test composite laminates were prepared from the prepregs in accordance with method EN2565 discussed above. MECHANICAL RESULTS
[0108] The composite test laminates were subjected to mechanical testing, and the results are shown in Table 5. The mechanical results reported in Table 5 show that the introduction of polymeric hardening particles compared to MWCNTs in the matrix resin can produce improvements significant in CAI (at 30 J) and GIc values compared to otherwise identical materials modified with MWCNTs only (Control 4) or which lack polymeric hardening particles (Control 2).TABLE 5. MECHANICAL RESULTS

[0109] The simultaneous improvement in the two mechanical properties - CAI [30 J] and Gic - is believed to be the result of a synergistic effect between MWCNTs and polymeric hardening particles.
[0110] Figures 9A and 9B show that the addition of MWCNTs to laminates without polymeric hardening particles (Control 4) did not produce any significant improvement in CAI and GIce performance compared to the unmodified laminate (Control 2).
[0111] Figures 10A and 10B show that the addition of MWCNTs in laminates containing polymeric hardening particles (Laminates 4a, 4b, 4c and 4d) resulted in higher CAI and GIc values compared to the same laminates without MWCNTs (Laminates 2a, 2b, 2c and 2d). Figure 11 is a micrograph image of a cross-section of the cured laminate 4b, which contains MWCNTs and polyphthalamide particles (Particle B). As can be seen from Figure 11, the polymer particles are dispersed in the resin-rich layer, creating a well-defined ductile interlaminar region between the fiber layers. ELECTRICAL CONDUCTIVITY RESULTS
[0112] Table 7 reports the mean values of conductivity in the z-direction of laminates modified with MWCNT with interlaminar polymeric particles (Laminates 4a, 4b, 4c and 4d) and the laminate without interlaminar polymeric particles (Control 4).TABLE 7. RESULTS OF ELECTRICAL CONDUCTIVITY CC in the Z direction

[0113] It was observed that the addition of Particle A, which is soluble in the matrix resin (3a) upon curing, has a neutral effect on conductivity values in the z direction. Figure 12 is a cross-sectional micrograph of the cured laminate 4a, which contains MWCNTs and aromatic polyamide particles (Particle A).
[0114] Surprisingly, the addition of insoluble particles (Particles B and D) and expandable particles (Particle C) yielded better electrical performance than that of laminate modified with only MWCNTs (Control 4). This result is surprising given that the addition of insulating elements in the interlaminar region was traditionally expected to substantially decrease the volumetric conductivity of the cured composite as in the case of corresponding laminates without MWCNTs (see Example 1, Table 3m Laminates 2a, 2b, 2c and 2d ). It is notable that such improvement has been achieved by reducing the overall MWCNT content in the resin system from 1.55% w/w (Control 3) to 1.35% w/w (Matrix resins 3b, 3c and 3d).
[0115] Figure 13 shows the conductivity in the z direction for the Control 2, 2b, 2c, 2d, Control 4, 4b, 4c and 4d laminates. As shown in Figure 13, the addition of insoluble and intumescent crosslinked particles reduced the z-direction conductivity of unmodified laminates, while the addition of the same polymeric hardening particles in laminates that include MWCNTs resulted in improved z-direction conductivity values. 3EFFECT OF SOLUBLE ELASTOMERIC PARTICLES IN COMPOSITE MATERIALS MODIFIED WITH CNT
[0116] A matrix resin with insoluble elastomeric particles (Control 5) was prepared according to the formulation shown in Table 8. The same curable resin composition was modified by dispersing 1.35% by weight of carbon nanotubes with multiples walls (MWCNTs) that have carbon purity >98%, an average diameter of 15 nm, and an average length of about 1 mm. The MWCNT modified resin composition (5a) is shown in Table 8. All amounts are shown in percent by weight (% by weight/weight) based on the weight of the formulation. TABLE 8. CURABLE MATRIX RESIN COMPOSITIONS

[0117] In Table 8, Araldite® PY 306 is a Bisphenol F triglycidyl ether resin available from Huntsman, Araldite® MY 0510 is a p-aminophenol resin triglycidyl ether resin available from Huntsman, and SUMIKAEXCEL 5003P is a polymer of polyethersulfone available from Sumitomo ChemicalCo. Particle E is a carboxyl functional elastomer in powder form with a glass transition temperature of approximately -5°C and an average particle size of 50 microns, and is sold under the trade name DuoMod® DP5045 from ZeonChemicals L.P.
[0118] The resin matrices were prepared by dispersing the thermoplastic 5003P in the epoxy constituents and heating at 125 °C for approximately 1 hour to dissolve the thermoplastic 5003P. The resulting mixture was cooled to 80°C, and then the remaining constituents were added and thoroughly mixed.
[0119] The resin compositions were then used to produce different unidirectional prepregs (UD). Each of the curable resin compositions disclosed in Table 8 was used to make a resin film by coating the resin composition onto a release paper. Then, two such resin films were laminated onto both sides of a continuous layer of unidirectional carbon fibers (IMS65E from TohoTenax, USA), with the aid of heat and pressure, to form a UD prepreg. Each resulting prepreg had an average FAW (fiber weight) of 197 gsm and 35% weight/weight resin content based on total prepreg weight. Test composite laminates were prepared from the prepregs in accordance with method EN2565 discussed above. MECHANICAL RESULTS
[0120] The composite test laminates having Particles E and MWCNTs were subjected to mechanical testing, and the results are shown in Table 9. The mechanical results reported in Table 9 show the introduction of insoluble elastomeric particles compared to MWCNTs in the resin. matrix can produce significant improvements in CAI (at 30 J) and GIc values compared to otherwise identical materials modified with only MWCNTs (Control 4, as disclosed in Example 2, Table 5) or a material without MWCNTs or hardening particles polymeric (Control 2, as disclosed in Comparative Example 1, Table 2).TABLE 9. MECHANICAL RESULTS

[0121] The simultaneous improvement in the two mechanical properties - CAI [30 J] and Gic - is believed to be the result of a synergistic effect between MWCNTs and polymeric hardening particles. ELECTRICAL CONDUCTIVITY RESULTS Table 10 reports the mean z-direction conductivity values of composite test laminates prepared from prepregs comprising E particles according to Control 5 and 5a resin compositions. TABLE 10. RESULTS OF ELECTRIC CONDUCTIVITY CC in direction

[0122] The DC electrical conductivity in the Z direction of composite test laminates containing insoluble elastomeric particles (E-Particles) but not MWCNTs is equal to 0.56 S/m (Control 6). The DC electrical conductivity in the Z direction of composite test laminates containing MWCNTs only and without interlaminar polymer particles is 6.00 S/m (Control 4). Surprisingly, the addition of insoluble particles (E-Particles) produced better electrical performance (8.25 S/m) than that of the laminate modified with only MWCNTs (6.00 S/m). This result is surprising given that the addition of insulating elements in the interlaminar region was traditionally expected to substantially decrease the volumetric conductivity of the cured composite as in the case of corresponding laminates without MWCNTs (Table 10, Control 2 and Control 6). has been achieved by reducing the overall MWCNT content in the resin system from 1.55% w/w (Control 4) to 1.35% w/w (Laminates 6a).

权利要求:
Claims (15)
[0001]
1. Curable composite material, characterized in that it comprises: at least two layers of reinforcing fibers impregnated with a curable matrix resin; and at least one interlaminar region formed between adjacent layers of reinforcing fibers, wherein the interlaminar region comprises (i) nanosized carbon-based structures dispersed in a curable matrix resin, and (ii) insoluble polymeric stiffening particles incorporated therein curable matrix resin, where nanosized carbon-based structures have at least one dimension less than 100 nm (0.1 µm), polymeric hardening particles have an average particle size (d50) that is at least 100 times larger that the smallest dimension of the nanosized carbon-based structures, and the average particle size is within the range of 10 to 100 µm, the polymeric hardening particles are insoluble in the matrix resin in the interlaminar region during the curing of the composite material and remain as discrete particles after curing, upon curing, the composite material exhibits electrical conductivity in the z direction greater than 1 S/m, Resistance to Com pressure After Impact (CAI), after impact at 30 J, greater than 250 MPa as measured in accordance with ASTM7136/37, and mode I interlaminar fracture strength (GIc) greater than 300 J/m2 as measured accordingly with the EN6033 standard.
[0002]
2. Curable composite material according to claim 1, characterized in that the polymeric hardening particles are insoluble thermoplastic particles comprising at least one thermoplastic selected from the group consisting of: polyimide, polyamideimide, polyamide, polyphthalamide, polyetherketone . polyetherketone, polyetherketone, polyaryletherketones, polyphenylenesulfide, liquid crystal polymers, copolymers thereof and derivatives thereof.
[0003]
3. Curable composite material according to claim 1, characterized in that the hardening insoluble polymeric particles are insoluble elastomeric particles comprising at least one polymer or polymeric material selected from the group consisting of: crosslinked polybutadiene, polyacrylic, polyacrylonitrile, polystyrene, copolymers thereof and derivatives thereof.
[0004]
4. Curable composite material according to claim 1, characterized in that the hardening insoluble polymer particles are crosslinked particles, each particle comprising one of: (a) a crosslinking network created by crosslinking a crosslinkable thermoplastic polymer that has one or more groups reactive with a crosslinking agent that is chemically reactive to the reactive groups, and (b) an interpenetrating polymeric network (IPN) comprising thermoplastic polymer chains intertwined with an independent crosslinking network, in which the IPN is created reacting at least one compound that has one or more reactive groups, a crosslinking agent that is chemically reactive to the reactive groups, and a thermoplastic polymer.
[0005]
5. Curable composite material according to any of the preceding claims, characterized in that the nanosized carbon-based structures are selected from the group consisting of: carbon nanotubes (CNTs), carbon nanofibers, carbon nanostrings, nanolaces carbon, carbon nanofibrils, carbon nanoneedles, carbon nanosheets, carbon nanorods, carbon nanocones, carbon nanorolls (roll-like shapes) and carbon nanoohms, carbon black, nanoplatelets or graphite nanodots , graphenes and their combination.
[0006]
6. Curable composite material according to any one of the preceding claims, characterized in that the interlaminar region is free of any soluble thermoplastic particles that dissolve in the matrix resin upon curing.
[0007]
7. Curable composite material according to any one of the preceding claims, characterized in that the hardening particles are substantially spherical and form a single layer of particles in the interlaminar region so that the interlaminar region has a depth that is defined by the diameters of the hardening particles.
[0008]
8. Curable composite material according to any one of the preceding claims, characterized in that the curable matrix resin that impregnates the reinforcing fibers and the curable matrix resin in the interlaminar region comprise one or more thermosetting resins that are common to both the matrices.
[0009]
9. Curable composite material according to any one of the preceding claims, characterized in that the curable matrix resin impregnating the reinforcing fibers is substantially the same as the curable matrix resin in the interlaminar region without the nanosized structures and particles of hardening.
[0010]
10. Curable composite material according to any one of the preceding claims, characterized in that the curable matrix resin that impregnates the reinforcing fibers and the curable matrix resin in the interlaminar region comprise uniformly dispersed nanosized carbon-based structures.
[0011]
11. Curable composite material according to any of the preceding claims, characterized in that the polymeric hardening particles are substantially spherical in shape, and the nanosized carbon-based structures are carbon nanotubes, in which the polymeric hardening particles have an average particle size (d50) at least 100 times the diameter of carbon nanotubes.
[0012]
12. A method for making a curable composite material, characterized in that it comprises: (a) dispersing nanosized carbon-based structures and polymeric hardening particles in a first curable matrix resin to form a curable conductive matrix resin;(b ) forming at least one resin film from the curable conductive matrix resin; (c) forming a structural layer comprising a layer of reinforcing fibers impregnated with a second curable matrix resin which is free of polymeric hardening particles; and (d) placing at least one resin film on an outer surface of the structural layer, where nanosized carbon-based structures have at least one dimension less than 100 nm (0.1 µm), polymeric hardening particles have an average particle size (d50) that is at least 100 times larger than the smallest dimension of the nanosized carbon-based structures, and the average particle size is within the range of 10 to 100 µm, and the polymeric hardening particles are insoluble in the matrix resin in the interlaminar region during the curing of the composite material and remain as discrete particles after curing.
[0013]
13. Method according to claim 12, characterized in that said second curable matrix resin further comprises nanosized carbon-based structures.
[0014]
14. A method for making a curable composite material, characterized in that it comprises: (a) dispersing nanosized carbon-based structures and polymeric hardening particles in a curable matrix resin to form a curable matrix resin; (b) forming a composite material by impregnating a layer of reinforcing fibers with said curable matrix resin such that polymeric stiffening particles are present on at least one side of the layer of reinforcing fibers, wherein nanosized carbon-based structures have at least one dimension less than 100 nm (0.1 µm), polymeric hardening particles have an average particle size (d50) that is at least 100 times larger than the smallest dimension of the nanosized carbon-based structures, and the Average particle size is within the range of 10 to 100 µm, and polymeric hardening particles are insoluble in the matrix resin in the interlaminar region during curing of the composite material and remain as discrete particles after curing.
[0015]
15. Method for fabricating a composite structure, characterized in that it comprises: (a) laminating at least two of the curable composite material produced from the method, as defined in any one of claims 12 to 14, in a stacking arrangement, to form a lamination; and (b) curing the lamination, in which, after curing, the cured composite structure exhibits electrical conductivity in the z direction greater than 1 S/m, Compressive Strength After Impact (CAI), after impact at 30 J, greater than 250 MPa as measured in accordance with ASTM7136/37, and mode I interlaminar fracture toughness (GIc) greater than 300 J/m2 as measured in accordance with EN6033.

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同族专利:

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公开号 | 公开日

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TWI649196B|2019-02-01|

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ES2651965T3|2018-01-30|

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EP3080196A2|2016-10-19|

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GB201322093D0|2014-01-29|

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AU2014384605B2|2017-09-14|

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EP3080196B1|2017-09-13|

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JP6585596B2|2019-10-02|

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AU2014384605A1|2016-06-02|

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TW201532810A|2015-09-01|

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CN105813833B|2017-09-01|

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WO2015130368A3|2015-11-12|

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法律状态:
2018-02-20| B08F| Application dismissed because of non-payment of annual fees [chapter 8.6 patent gazette]|

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2018-03-06| B08G| Application fees: restoration [chapter 8.7 patent gazette]|

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2019-12-17| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2021-07-06| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2021-08-24| 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 05/12/2014, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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GB1322093.4|2013-12-13|

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GBGB1322093.4A|GB201322093D0|2013-12-13|2013-12-13|Compositive materials with electrically conductive and delamination resistant properties|

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PCT/US2014/068693|WO2015130368A2|2013-12-13|2014-12-05|Composite materials with electrically conductive and delamination resistant properties|

---