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    • 专利摘要:
    thermoplastic laminated compound, compound structure, laminated compound, and method for forming a laminated compound some embodiments in this document are directed to a thermoplastic composite structure with at least one structural layer of fiber-reinforced thermoplastic resin and at least one adjacent hardening layer to the surface of the structural layer. the hardening layer is configured to create an interlaminar region in a laminated compound and can take the form of a polymer film, woven or non-woven fibrous materials, free particles, a polymer layer or non-woven web with hardening particles dispersed in it , sheet or metal mesh.
    公开号:BR112014003350B1
    申请号:R112014003350-1
    申请日:2012-08-01
    公开日:2020-02-18
    发明作者:Scott Alfred Rogers；James Francis Pratte
    申请人:Cytec Technology Corp.；
    IPC主号:
    专利说明:

    “THERMOPLASTIC LAMINATE COMPOUND, COMPOUND STRUCTURE, AND, LAMINATE COMPOUND” cross-reference to related orders [0001] This order claims priority to U.S. Temporary Order No. 61 / 528,561, filed on August 29, 2011.
    fundamentals [0002] Conventionally, thermoplastic hardening agents have been added to thermoset resin systems to give strength and to attenuate the fragility of the composite material that would be present without thermoplastic hardening agents. For example, thermoplastic curing particles or thermoplastic curing agents have been used with structural compounds to improve the strength of thermoset resin-based systems. In contrast to thermoset resin systems, thermoplastic resin systems have not normally been reinforced with additional hardening material, since thermoplastic systems are believed to have sufficient strength properties. However, aerospace and other industries have influenced the evolutionary development of composite materials requiring improved performance, for example, the better rigidity of thermoplastic material.
    [0003] One of the many benefits of thermoplastic compounds is the high matrix stiffness that the polymer produces. The interlaminar region is usually very small or non-existent in consolidated stratifications using the current state of the pre-impregnated thermoplastic compounds in the art. This configuration can allow for easier transmission of the impact situation in the next fold that spreads the damage area.
    [0004] Conventional laminates require further improvement. Conveying improved strength or compression after impact (CAI) performance of a consolidated laminate would be a useful advance in technique and could find rapid acceptance in large commercial transport and / or industries
    Petition 870190132519, of 12/12/2019, p. 7/44 / 22 military aerospace, among other industries that require composite materials to perform in demanding environments.
    summary of the invention [0005] It has been found that by increasing the size of the interlaminar region and the content of thermoplastic laminates, the compression after impact (CAI) performance is better. In addition, to improve the hardness of the CAI of the laminate, it is also necessary to address the remaining weakness within the inter-fold regions of the structure.
    [0006] To address these issues, some modalities in this document are directed to a consolidated or unconsolidated thermoplastic composite structure with at least one structural layer composed of fibers impregnated with a reinforcing thermoplastic resin matrix and at least one hardening layer on a structural layer surface. The hardening layer is configured to create an interlaminar region in a laminated compound and can take the form of a polymer film, woven or non-woven fibrous materials, free particles, a polymer layer or non-woven web with hardening particles dispersed in it , mesh or sheet metal not impregnated or impregnated.
    [0007] A plurality of such a structural layer is placed in a stacking arrangement such that there is a hardening layer positioned between two adjacent structural layers. Due to this configuration, the CAI strength of the composite laminate, upon consolidation, is greater than the laminate even without the hardening layers.
    brief description of the drawings [0008] Figure 1 shows the DSC curve of a control laminate formed with DSE Cypek ™ matrix base, reinforced with unidirectional carbon fiber tapes.
    [0009] Figure 2 shows the DSC of an improved laminate formed with DSE Cypek ™ matrix base, reinforced with unidirectional ribbons of
    Petition 870190132519, of 12/12/2019, p. 8/44 / 22 carbon fiber and glass hardening layers.
    [00010] Figure 3 is a micrograph showing the interlaminar region of the control laminate formed with DSC matrix base from APC ™ Cypek ™, reinforced with unidirectional carbon fiber tapes.
    [00011] Figure 4 is a micrograph showing the interlaminar region of the laminate formed with Cypek ™ DSE matrix base, reinforced with unidirectional carbon fiber tapes and glass hardening layers. [00012] Figure 5 is a micrograph showing the interlaminar region of a laminate formed with Cypek ™ DSE matrix base, reinforced with unidirectional carbon fiber tapes and Cypek ™ DSE hardening film.
    detailed description of preferred embodiments [00013] In contrast to conventional composite materials containing thermosetting resin systems hardened with interlaminated particles or layers that can be crosslinked, the thermoplastic resin matrix for the structural layer in this document does not depend on crosslinking with hardening material for form a rigid layer. In some respects, the rigid layer does not melt or has a high melting viscosity at processing temperature, and thus the hardening material does not migrate or mix extensively with the thermoplastic matrix resin in the fiber-reinforced structural layer. As a result, the resin in the thermoplastic matrix of the fiber-reinforced structural layer forms a well-defined boundary in the interlaminar region, which in turn results in an inter-layer (or inter-folds) that provides discrete spacing between adjacent structural layers. In contrast, some resin-based thermosetting compounds have a less well-defined interlaminar region, because the tempered layer may form a less discreet layer due to the cross-linking between the resin and the
    Petition 870190132519, of 12/12/2019, p. 9/44 / 22 hardening. Former thermosetting resin-based compounds without hardening agents had little interlaminar area. However, stiffeners have been used in some thermosetting resin-based compounds to create the inter-fold region. However, hardening materials that may be suitable for thermoset resin systems may be incompatible with thermoplastic resin systems. Specifically, resin-based thermoplastic compounds generally consolidate at temperatures higher than resin-based thermoset compounds and in some cases almost twice the typical cure temperature of thermoset resin. Thus, hardening materials used in thermo-rigid compounds that melt and potentially thermally degrade before the processing temperature of thermoplastics would not be compatible.
    [00014] The processing temperature refers to operating temperatures when laminating the thermoplastic structural layers, which is normally within the range of 20 ° C to 40 ° C above the peak melting point in a Scanning Calorimetry scan. Differential (DSC) for a semicrystalline polymer and 80 ° C to 150 ° C above the glass transition temperature (Tg) for an amorphous polymer.
    [00015] The laminate or thermoplastic compound in this context includes a plurality of structural layers in a stacking arrangement, each composed of reinforced fibers impregnated with a thermoplastic resin matrix. The resin matrix includes one or more thermoplastic resins, as the main component. Thus, the resin matrix has thermoplastic properties; however, the resin matrix may contain small amounts of additives such as plasticizers, rheology modifiers, inorganic fillers, etc. For example, inorganic filler particles such as mica, silica, silicon carbide, aluminum nitride, boron nitride, aluminum oxide can be mixed with the thermoplastic resin. Suitable thermoplastic resins include: polyetherimide
    Petition 870190132519, of 12/12/2019, p. 10/44 / 22 (PEI), polyaryethylketone (PAEK), polyphenylene sulfide (PPS), polyamide (Nylon) and their combinations. polyarylethylketones (PAEK) are crystalline polymers and may include, but are not limited to, polyether ketone (PEK), polyetheretherketone (PEEK), polyether ketone ketone (PEKK) and polyetherketone ketone (PEKEKK). These thermoplastic resins have an inherent strength and, therefore, typical thermoplastic resins have not been conventionally considered a material that needs hardening. This stiffness imparts good impact performance to the finished laminate. However, it has been found that the hardening layers can be added to thermoplastic compounds to further improve the stiffness characteristics. The hardness of the compound can be measured as the Compression After Impact (CAI) performance using the ASTM D7136 test method. In some cases, CAI performance greater than 50 KSI can be obtained. More specifically, CAI performance can exceed 55, 60, 65 or 70 KSI. For example, laminates formed from semi-crystalline CYPEK ®DS-E unidirectional tapes and hardening layers can provide CAI of 55 KSI. Unidirectional tape refers to a layer of fibers impregnated with resin, where the fibers are aligned along one direction.
    [00016] Commercially available PAEK polymers include APC-2® PEEK® CYPEK-DSM or DSE or FC and CYPEK®-HTE, which are all commercially available from CytecEngineered Materials / Cytec Industries Inc. Cypek ™ DSE, DSM, FC, HTE are PEKK polymer grades from Cytec Industries Inc. DS meets Declaration specification, M corresponds to molding. HTE corresponds to high temperature extrusion, and FC corresponds to “rapid crystallization”.
    Hardening materials [00017] Hardening layers can take the form of continuous or perforated polymer films, fibrous woven or non-woven materials, free particles, a polymer layer containing particles in it
    Petition 870190132519, of 12/12/2019, p. 11/44 / 22 dispersed, non-woven veil of polymeric fibers arranged randomly containing hardening particles dispersed in them, impregnated or non-impregnated sheet or metal mesh. Suitable materials for the hardening layer include: high melting point and high molecular weight of thermoplastic polymers; plasticized thermoplastic polymers; high flow polymers; semi-crystalline or fast crystallizing thermoplastic polymers; polymer hybrids of the matrix resin; multipolymer alloys; thermoset polymers like polyamide; ceramics such as alumina oxide and silicate; metals such as copper, silver, titanium, aluminum and alloys thereof, and combinations of any of the above materials.
    [00018] The selection of material or material combination for the hardening layers depends on the configuration of the hardening layer and the thermoplastic resin matrix of the fiber-reinforced structural layer. For the polymer or web film containing curing particles, materials are selected to create a synergistic effect between the polymer or web film and the curing particles in the interlaminar region.
    [00019] High melting point thermoplastic polymer refers to any thermoplastic polymer that has a melting temperature (Tm) greater than or equal to 280 ° C, measured by DSC and a processing temperature (Tprocess) greater than or equal to 300 ° C.
    [00020] High molecular weight thermoplastic polymer refers to the polymer with an average molecular weight (MW) above 10,000.
    [00021] High flow polymer refers to polymers with a melt viscosity of less than 600 Pa-s at an apparent shear rate of 10 s -1 at melt processing temperature, for example, Cypek ™ DS- M at 340 ° C.
    [00022] Semicrystalline polymer refers to any thermoplastic polymer that exhibits an exothermic melt, as measured by DSC, for example, PEEK.
    Petition 870190132519, of 12/12/2019, p. 12/44 / 22 [00023] Rapid crystallization polymer refers to semicrystalline thermoplastic polymers that can reach greater than or equal to 15% crystalline content after being cooled to 10 ° C / min or higher, for example, PEEK.
    [00024] Hybrid polymer matrix matrix refers to a copolymer or polymer transplanted into the base matrix polymer.
    [00025] Multipolymer alloy refers to a mixture of compatible or incompatible polymers of two different polymers.
    [00026] Plasticized thermoplastic polymer refers to a thermoplastic polymer that has plasticizer mixed in it. An example is diphenylsulfone mixed in PEEK.
    [00027] For the thermoplastic and web layer containing hardening particles, the particles include microspheres such as glass micro grains or ceramic microspheres (for example, Zeospheres). Alternatively, the curing particles can be formed by a thermoplastic polymer other than the thermoplastic layer or the thermoplastic web in which the particles are dispersed.
    [00028] In certain embodiments, two or more hardening materials can be extruded and then ground to form particles. These particles are then placed in the structural layer. Mixtures of different types of particles with different particle sizes can be used as hardening materials. Particles and respective mixtures can be sprinkled on a surface of a structural layer and melted to form the hardening layer. For example, PEEK particles can be mixed with aluminum silicate or other type of inorganic particle (s) and then applied by spraying on the structural layer, followed by melting lamination, optionally, with application of heat. In another embodiment, two different thermoplastic polymer particles from different melting points and / or melting viscosity are
    Petition 870190132519, of 12/12/2019, p. 13/44 / 22 rolled at the lowest melting temperature of the two polymers. As an example, a mixture of Cypek ™ DSM particles (peak melting point = 300 ° C) Cypek ™ HTE particles and particles (peak melting point = 355-360 ° C) are placed in the structural layer and then melted laminated at 340 ° C.
    [00029] In another embodiment, to increase the hardness and to create an inter-fold region, metallic particles can be deposited on one or both surfaces of the structural layer, as a unidirectional ribbon of unidirectional carbon fibers impregnated with thermoplastic polymer. Metallic materials can be irregular in shape, filamentous or spherical particles and have the added benefit of improving electrical conductivity in the compound.
    [00030] In modalities in which particles are used, the particles can be sized in micro size. Preferably, the particles have a particle size of greater than 3 microns.
    [00031] In another embodiment, the hardening layer is a metal mesh or sheet or a combination of metal mesh and metal sheet in a multilayer laminate. In a multi-layered structural layer reinforced with fiber, a plurality of such metallic hardening layer is present in the interlaminate regions.
    [00032] In another embodiment, the hardening layer is a glass fiber cloth. In addition, the glass fiber cloth can be subjected to Chemical Vapor Deposition (DCV) to deposit a very thin layer of metal such as aluminum for the glass fibers. The metal coating can each provide electrical conductivity for the inter-fold region. In addition, this metal coating can give electrical conductivity in the plane which helps in reducing the heat of the edge in the part of the compound (capacitive discharge in large compound structures, such as wing fuel tanks).
    Petition 870190132519, of 12/12/2019, p. 14/44 / 22 [00033] In another embodiment, the thermoplastic matrix resin and the hardening layer are made of the same thermoplastic resin, for example, PAEK.
    [00034] In some embodiments, a combination of a curing polymer and one or more of the curing particles can be used. For example, the particles could be composed in an extruder with the curing polymer to create a material for inter-laminar hardening. For example, particles or glass fibers composed in a PEEK or PEKK polymer to form pellets or a film. Subsequently, the pellet or film can be applied to the structural layer through lamination or another process. As another example, Cypek ™ DS-M particles (melting point peak = 300 ° C) and a PEEK resin (peak melting point = 340 ° C) can be combined, extruded and applied as a film and laminated to the structural layer . Likewise, PEEK particles and a Cypek ™ DS-M resin can be combined, extruded and applied as a film and laminated to the structural layer, in which PEEK particles are only partially melted into the completely melted Cypek ™ DS-M. Combinations of larger melting polymer particles with low melting polymer matrices can be used as Cypek ™ FC (melting point peak = 338 ° C) or Cypek ™ HT-E particles (melting point peak = 355 ° C - 360 ° C) on a Cypek ™ DS-M resin.
    [00035] In some embodiments, the hardening layer is at least semi-crystalline throughout the layer - meaning that the layer is semi-crystalline throughout the layer, or contains crystalline portions uniformly dispersed throughout the layer. Thus, an amorphous layer adjacent to a crystalline layer would not be considered at least semi-crystalline at all because the material layer is predominantly amorphous in parts thereof. Specifically, the amorphous portion would not be considered at least semi-crystalline in that part and,
    Petition 870190132519, of 12/12/2019, p. 15/44 / 22 therefore, it would not be considered at least semi-crystalline in the entire layer. In some embodiments, the structural layers are unidirectional tapes containing semicrystalline polymers and the hardening layers are made of semicrystalline polymers. Generally, amorphous resin is more susceptible to solvent attack, which is not a desirable effect. The two semicrystalline polymers can have different melting points and different crystallization rates based on their chemical formulation so that, for a given cooling rate, each semicrystalline polymer will yield a different crystalline content in the other layer with the lower layer of the content crystalline polymer (slower crystallization rate) providing the hardening layer. It is possible to use any polymers of higher or lower melting point in harmony to harden the material.
    [00036] The hardening layer can also be in the form of fabric fibers (for example, a woven fabric) or non-woven fibers (for example, a veil or mat of randomly arranged fibers). If the fibers are present, they are preferably generally at least half the diameter of the structural reinforcement fibers in the structural layer. In some cases, hardening fibers and structural fibers have approximately the same diameter. For example, a reinforcing or structural fiber like a carbon fiber can have a filament diameter of about 7 pm, while a glass fiber to be used as a hardening material can have a filament diameter of about 5-9 pm. It is expensive to make hardening fibers of relatively small diameter compared to hardening fibers of approximately the same diameter as structural fibers. Thus, fibers of sub-micron diameter are generally not preferable.
    [00037] In general, more crystalline thermoplastics (ie, with greater crystallinity) produce greater resistance to compression and less resistance
    Petition 870190132519, of 12/12/2019, p. 16/44 / 22 to the impact. In contrast, amorphous thermoplastics produce less resistance to compression and greater resistance to impact. In aspects of this document, crystallinity is useful for providing resistance to solvent degradation. A higher crystallinity value (up to 35%) improves the performance of the polymer against this solvent attack. Crystallinity is measured by DSC. This type of thermoplastic is suitable for the resin matrix of the structural layer and for the hardening layers.
    [00038] It is known that the melting point and the crystallinity rate of some PAEK polymers such as PEKK and PEKEKK can be changed by adjusting the terephthaloyl (T), the proportion of isophthaloyl (I) (ratio T: I). In the current PEKK synthesis, T and I are controlled by the relative amounts of terephthaloyl chloride and isophthaloyl chloride to make a copolymer block. Without wishing to be bound by theory, it is believed that increasing the number of segments I places more folds in the main polymer structure, thus decreasing the activation energy and rate for a chain rotation to reach the minimum energy configuration for formation crystalline. This results in a lower melting temperature and a slower crystallization rate.
    [00039] For most of the modalities discussed above, the content of the hardening material is up to 20% by weight, based on the total weight of the matrix resin in the laminate. The amount of hardening material is sufficient to create a distinct interlaminar region between adjacent layers of reinforced resin-impregnated fibers.
    [00040] When the thermoplastic resin matrix of the structural layers is based on PAEK polymers (for example, PEEK or PEKK), particularly suitable curing materials include (i) polymer films made of PEKK, PEEK, PEK or polyamide; (ii) glass fibers, carbon fibers or aramid fibers in the form of chopped fibers, non-woven mat or fabric (for example, glass fiber cloth with an area of 0.55 oz / yd 2 in weight); (iii)
    Petition 870190132519, of 12/12/2019, p. 17/44 / 22 particles made of polyimide, PEEK, PEKK, PEK, or glass and mixture of particles (iv) foil, mesh, flakes, fibers or particles made of aluminum, copper, titanium, nickel or a combination thereof.
    [00041] When the thermoplastic resin matrix of the structural layers is based on polyphenylene sulfide polymer (PPS), particularly suitable hardening materials include (i) polymer films made of PPS, PEEK, PEK, PEKK, PEKEKK, polyamide or polyamide ( Nylon); (ii) glass fibers, carbon fibers or aramid fibers in the form of chopped fibers, non-woven mat or fabric; (iii) particles made of PEEK, PEKK, PEK, PEKEKK, or glass and mixture of particles (iv) metal foil, mesh, flakes, fibers or particles of aluminum or stainless steel.
    [00042] When the hardening material includes foil or mesh, the foil or mesh can be incorporated into a hardening polymer such as PEEK or PEKK.
    [00043] In one embodiment, the structural layer is composed of fibers impregnated with a matrix of reinforcing thermoplastic resin, and the hardening layer is a veil of thermoplastic fibers randomly arranged having thermoplastic particles dispersed in this, where the thermoplastic resin matrix, the veil and particles are made of different thermoplastic materials. As an example, the structural layer is composed of reinforcement fibers impregnated with PPS, the veil is composed of PEKK fibers and the particles are made of PEEK or, alternatively, the veil is composed of PEEK fibers and the particles are made of PEKK .
    Thermoplastic Structural Laminates and Layers [00044] Adding a hardening material to the fiber reinforcing the composite layer such as unidirectional fiber reinforced composite tape, that is, a product with resin and fibers, can be done through various applications, such as such as hot rolling, surface application methods, including electrostatic applications, of the
    Petition 870190132519, of 12/12/2019, p. 18/44 / 22 hardening after the uni-tape is produced. This process will keep the hardening material on the outer perimeter of the material where it is most effective. Further increases in the percentage, by weight, of material hardening may require additional resin film to avoid scarcity, that is, a situation in which insufficient laminate resin will have voids due to high volumes of fibers locally. This effort showed low favorable porosity within the laminate, but due to the resin placed away from the unidirectional tape.
    [00045] In certain modalities, the hardness of the unidirectional thermoplastic tape made by the methods of impregnation of aqueous paste and melting is increased by the stratification of the hardening layer to the product online.
    [00046] The term fiber as used here has its usual meaning as known to those skilled in the art and may include one or more fibrous materials, adapted for the reinforcement of the compounds. Fibers can take the form of any of the particles, flakes, whiskers, short fibers, continuous fibers, sheets, tarpaulins and respective combinations. Continuous fibers can also adopt any of the unidirectional, multidimensional configurations (for example, bi or three-dimensional), non-woven, woven, knitwear, embroidery, coverings and braids, as well as structures of spiral carpet, felt carpet and patchwork carpet. Fabric fiber structures can include a plurality of fabric fiber with less than about 1000 filaments, less than about 3000 filaments, less than about 6000 filaments, less than about 12000 filaments, less than about 24000 filaments, less than about 48000 filaments, less than about 56000 filaments, less than about 125000 filaments and more than about 125000 filaments. In other embodiments, the fibers can be placed in position by cross-points of the fiber, weft insertion points of the mesh or a small amount of resin, such as a
    Petition 870190132519, of 12/12/2019, p. 19/44 / 22 dimensioning. The reinforced fibers in the structural layer preferably have a tensile strength greater than 3500 MPa. The content of the reinforcing fibers in the structural layer is preferably at least 55% by weight, based on the total weight of the structural layer.
    [00047] In some respects, the fibers used in the structural component are generally of uniform diameter and generally of conventional diameter, such as about several micrometers at about the millimeter gap. Thus, in some respects, small diameter fibers can be expensive and can be difficult to discern an interlaminar region and therefore do not provide a discrete interlaminar region that is useful for the laminate disclosed in this document.
    [00048] The composition of the fibers can be varied as needed. Modalities of the fiber composition may include, but are not limited to, glass, carbon, aramid, quartz, basalt, polyethylene, polyester, poly-p-phenylene-polyphenol (PBO), boron, silicon carbide, polyamide and graphite and their combinations. In one embodiment, the fiber is carbon, fiberglass, aramid or other thermoplastic materials. Reinforcement fibers can be organic or inorganic. In addition, fibers can include textile architectures, including those that are or are not continuous in shape.
    [00049] Structural fibers may include unidirectional tape or net, fiber, preg, or cloth and non-woven materials such as a rug or a veil. Fiber-reinforced composite materials are generally categorized as tape, woven cloth, non-woven cloth, paper and their mixtures. Ribbon generally refers to uniaxial reinforcement fibers that extend along a single axis of the strip material. The term cloth generally refers to reinforcement fibers placed along at least two different axes within the strip material. The cloth is commercially available as bi-axial, triaxial and quad-axial, indicating fibers extending in two, three or four different axes, respectively. The fibers can optionally be woven
    Petition 870190132519, of 12/12/2019, p. 20/44 / 22 with each other, or can be manufactured as a non-woven cloth. A wide range of compound reinforcing fibers are commercially available, such as, for example, carbon fibers, Kevlar ® fibers, glass fibers and aramid fibers.
    [00050] The terms matrix, resin, and matrix resin, as used in this document, refer to the composition of resin in the structural layer and may include small amounts of optional additives, such as inorganic fillers.
    [00051] The term pre-impregnated as used in this document includes a sheet or a layer of fibers, which have been impregnated with a matrix material within at least part of its volume. Typically, a prepreg is a malleable shape that is ready for molding into a particular shape and curing for the final part of the compound. Such composite parts are commonly used in the manufacture of structural load parts and especially aerospace composite parts, such as wings, fuselages, bulkheads, control surfaces, motorcraft and other applications where impact and hardness are important.
    [00052] The term intercalated as used here has its usual meaning as known to those skilled in the art and includes a layer placed between other layers of. In one embodiment, the interlayer can be positioned in the middle of a composite plane. For example, interlayer is commonly found between layers of structural fibers.
    [00053] Interlaminar refers to the region between two adjacent layers.
    [00054] A laminate can be composed of several structural layers of fiber reinforced resin or prepregs.
    [00055] The term layup as used here has its usual meaning, as known to those skilled in the art may include one or more of the prepregs that are placed adjacent to each other. In certain
    Petition 870190132519, of 12/12/2019, p. 21/44 / 22 modalities, the prepregs within the layout can be positioned in a selected orientation in relation to each other. In another embodiment, prepregs, optionally, can be sewn together with a segmentation material to inhibit the relative movement of a selected orientation. In additional embodiments, layups can include any combination of fully impregnated prepregs, partially impregnated prepregs and perforated prepregs as discussed in this document. Layups can be manufactured using techniques that can include, among others, manual layup, automated tape layup (ATL), advanced fiber placement (AFP) and filament winding. The layups can then be cured, such as by autoclaving, to form a composite article, in which the hardening particles are located in the interleaved and provide greater hardness and damage the tolerance of the composite article due to the remaining discrete particles, even after the process of cure.
    [00056] The terms consolidated and unconsolidated as used here have their common meaning, as known to those skilled in the thermoplastics technique. Consolidation of melt-melting thermoplastics generally includes sufficient heating to deform the thermoplastic resin, resin consolidation and cooling. Hot rolling is a typical consolidation process.
    [00057] In some cases, the thermoplastic resin is solid at room temperature.
    [00058] In some respects, manufacturing methods include hot rolling of hardening to the outside of the unidirectional tape, which are typical methods used in the art.
    [00059] The terms approximately, approximately and substantially, as used in this document, represent an amount close to the indicated amount that still performs the function
    Petition 870190132519, of 12/12/2019, p. 22/44
    17/22 desired or achieves the desired result. For example, the terms approximately, about and '' substantially '' may refer to an amount that is within less than 10% of, within less than 5% of, within less than 1% of, within less 0.1% and within less than 0.01% of the declared quantity.
    [00060] The term at least a portion of as used in this document represents a quantity of a whole that comprises a quantity of the whole that can include the totality. For example, the term a portion of may refer to an amount that is greater than 0.01% of, greater than 0.1% greater than 1%, greater than 10%, greater than 20%, greater than 30 % of, greater than 40%, greater than 50%, greater than 60%, greater than 70%, greater than 80%, greater than 90% of, greater than 95% than, greater than 99% and 100% of the total.
    EXAMPLES
    Example 1 - Glass hardening [00061] A test laminate was formed by placing two folds of finished glass mesh BGF 104 1617 (a glass reinforcement of 5.55 oz / yd 2 ) between layers of unidirectional tapes containing Cypek ™ -DSE resin and Hexed AS4 carbon fibers, which are non-dimensioned carbon fibers normally used in 12K (12,000 filament) fibers with a nominal diameter of 7 μπι. No additional resin films were used. A control laminate, which is the same as the test laminate above, but is not tempered with fiberglass, has also been formed. CAI performance was measured using ASTM D7136. Tables 1 and 2 show the test results based on four test samples.
    Table 1 - Control
    Sample# Width in Depth in Depression Depth in Damaged area (3.0 dB loss) in 2 Damaged area (6.0 dB loss) in 2 1 3.9970 0.1749 0.0235 0.5392 0.4688
    Petition 870190132519, of 12/12/2019, p. 23/44
    18/22
    2 3.9965 0.1731 0.0238 0.5568 0.4688 3 3.9970 0.1744 0.0248 0.4016 0.3632 4 3.9980 0.1752 0.0238 0.5264 0.4560 Middle 3.9971 0.1744 0.0240 0.5060 0.4392 DetourPattern 0.0006 0.0009 0.0006 0.0707 0.0510 % VOC 0.02 0.53 2.37 13.97 11.62 Sample# Damaged area (18.0 dB loss) in 2 Energy ofImpact in * lbf Peak LoadIbf Ksi strength1 0.3840 1503 38983 55.82 0.3888 1501 37561 54.33 0.2832 1499 36731 52.74 0.3408 1505 36215 51.7Middle 0.3492 1502 37372 53.6DetourPattern 0.0490 3 1208 1.8% VOC 14.03 0.17 3.23 3.33
    Table 2 - Glass Hardened
    Sample# Width in Depth in Depression Depth in Damaged area (3.0 dB loss) in 2 Damaged area at (-6.0 dB loss) in 2 1 4.0010 0.1758 0.0253 0.8504 0.6336 2 4.0010 0.1755 0.0263 0.9504 0.7488 3 4.0015 0.1767 0.0260 0.6096 0.5312 4 4.0010 0.1737 0.0275 0.7184 0.5760 Middle 4.0011 0.1754 0.0263 0.7822 0.6224 DetourPattern 0.0002 0.0013 0.0009 0.1492 0.0941 % VOC 0.01 0.72 3.49 19.08 15.12 Sample# Damaged area (18.0 dB loss) in 2 Energy ofImpact in * lbf Ibf Peak Load Ksi strength1 0.4032 1503 39742 56.52 0.4848 1498 38904 55.43 0.4144 1503 38178 54.04 0.4016 1503 37943 54.6Middle 0.4260 1502 38692 55.1DetourPattern 0.0396 2 811 1.1% VOC 9.30 0.17 2.10 1.97
    Petition 870190132519, of 12/12/2019, p. 24/44
    19/22 [00062] Glass fabric has been found to improve CAI performance when compared to control laminate. The glass inter-hardening material increased from CAI to 57 KSI (normalized to cure layer thickness), an improvement of 2 ksi over the control product. The non-normalized CAI strength for laminated tempered glass was 55.1 ksi, while the non-normalized control was 53.6 ksi.
    [00063] FIG. 1 shows the DSC curve of the control laminate formed with DSE Cypek ™ matrix base, reinforced with unidirectional carbon fiber tapes, and FIG. 2 shows the DSC of the laminate with hardening layers of glass.
    [00064] FIG. 3 is a micrograph showing the interlaminar region of the control laminate formed with Cypek ™ DSE matrix base, reinforced with unidirectional carbon fiber tapes. FIG. 4 is a micrograph showing the interlaminar region of the laminate formed with Cypek ™ DSE matrix base, reinforced with unidirectional carbon fiber tapes and glass hardening layers.
    Example 2 - Thermoplastic Film Hardening [00065] The same method was used to form a test laminate, as discussed in Example 1 above, except a 0.25 mm Cypek ™ -DSE film was used as an interlayer for hardening instead fiberglass. CAI performance was measured using ASTM D7136. Tables 3 shows the test results based on four test samples.
    Table 3 - Hardened with Cypek ™ DSE
    Sample# Width in Depth in Depression Depth in Damaged area (3.0 dB loss) in 2 Damaged area (6.0 dB loss) in 2 1 4,0005 0.1795 0.0235 0.4800 0.4352 2 4,0003 0.1786 0.0280 0.5104 0.4560 3 4.0010 0.1785 0.0230 0.5136 0.4400 4 4,0002 0.1797 0.0250 0.5584 0.4880 Middle 4,0005 0.1791 0.0249 0.5156 0.4548 Detour 0.0004 0.0006 0.0022 0.0323 0.0239
    Petition 870190132519, of 12/12/2019, p. 25/44
    20/22
    Pattern% VOC 0.01 0.34 9.05 6.26 5.24 Sample Area Energy of Peak Load Force Nom Force # damaged (18.0 dB loss) in 2 Impact in * lbf Ibf ksi ksi 1 0.3280 1498 41334 57.6 60.3 2 0.3680 1498 38981 54.6 56.9 3 0.3616 1497 41272 57.8 60.2 4 0.3952 1507 36321 50.5 53.0 Middle 0.3632 1500 39477 55.1 57.6 DetourPattern 0.0276 5 2372 3.4 3.5 % VOC 7.60 0.31 6.01 6.15 6.00
    [00066] Cypek ™ DSE film has been found to improve compression after impact performance. 55.1 non-normalized ksi vs 53.6 non-normalized ksi for the control was achieved.
    [00067] FIG. 5 is a micrograph showing the interlaminar region of the laminate formed according to this Example.
    Example 3 - Glass and Thermoplastic Film Hardening [00068] Test laminates were made by the imposition of unidirectional AS4 carbon fiber tapes impregnated with Cypek ™ DSE resin and insertion of two layers of fiberglass fabric (0.72 oz / yd 2 ) and two 0.24 mil layers of Cypek ™ DSE film between adjacent unidirectional tapes. These were processed alongside a control laminate using the standard 710 ° F / 100 psi curing conditions. CAI strength was measured using ASTM D7136. Tables 4 and 5 show the test results based on four test samples.
    Table 4 - Control
    Sample# Eargura in Depth in Initial Impact Depth in Damaged area (-3.0 dB loss) in 2 Damaged area (6.0 dB loss) in 2 1 3.9987 0.1721 0.0218 0.5216 0.4608 2 3.9983 0.1734 0.0213 0.5968 0.5264 3 3.9975 0.1727 0.0220 0.5344 0.4704 4 3.9983 0.1737 0.0248 0.5840 0.4778
    Petition 870190132519, of 12/12/2019, p. 26/44
    21/22
    Middle 3.9982 0.1730 0.0225 0.5592 0.4840 DetourPattern 0.0005 0.0007 0.0016 0.0368 0.0292 % VOC 0.01 0.42 7.02 6.58 6.03 Sample# 9.6 Damaged area (18.0 dB loss) in 2 Impact energy in-lbs / inch Peak LoadIbf Ksi strength1 0.3648 1498 35663 51.82 0.4096 1506 34626 49.93 0.3666 1498 34308 49.74 0.3616 0 33233 47.9Middle 0.3756 1126 34458 49.8DetourPattern 0.0228 750 1000 1.6% VOC 6.06 66.66 2.90 3.26
    Table 5 - Hardened with glass / Cypek ™ PEKK
    Sample # Width in Depthin Depth of Depression after Impact in. Damaged area (3.0 dB loss) in 2 Damaged area (-6.0 dB loss) in 2 1 4,0005 0.2326 0.0263 0.4720 0.3952 2 4.0010 0.2338 0.0250 0.4800 0.4192 3 3.9978 0.2324 0.0235 0.5024 0.4432 4 3.9993 0.2321 0.0260 0.4272 0.3680 Middle 3.9997 0.2327 0.0252 0.4704 0.4064 DetourPattern 0.0014 0.0007 0.0013 0.0315 0.0322 % VOC 0.04 0.32 5.01 6.71 7.93 Sample # Damaged area (18.0 dB loss) in 2 Impact energy in-lbs / in Peak LoadIbf Strength ksi1 0.2800 1510 53303 57.32 0.3008 1507 48717 52.13 0.3216 1504 53708 57.84 0.2816 1507 49052 52.8Middle 0.2960 1507 51195 55.0DetourPattern 0.0195 2 2677 3.0% VOC 6.59 0.16 5.23 5.38
    [00069] For the control based on the Cypek ™ -DSE matrix, laminated with carbon fiber, the CAI force was 49.8 ksi after the energy test
    Petition 870190132519, of 12/12/2019, p. 27/44 / 22 1500 lb / inch impact. For the laminate hardened with fiberglass and Cypek ™ DSE film, an average of 55.0 ksi in CAI strength was obtained.
    [00070] Having described specific modalities within this disclosure, it should be understood that the description is not intended as a limitation since new modifications and variations may be apparent or may suggest to those who are versed in the technique. The present application is intended to cover all modifications and variations as they fall within the scope of the added claims.
    权利要求:
    Claims (19)
    [1]
    1. Thermoplastic laminated compound, characterized by the fact that it comprises:
    a plurality of structural layers in a stacking arrangement, each structural layer comprising reinforced fibers impregnated with a matrix thermoplastic resin; and a plurality of interlaminate regions, each being formed between two adjacent structural layers, each interlaminar region comprising a hardening material selected from:
    (a) non-woven or woven carpet comprising glass fibers or carbon fibers;
    (b) polyarylethylketone polymer film (PAEK) with hardening particles dispersed in it, where the particles are made of a material selected from: PAEK polymers that are different from the PAEK polymer of the PAEK polymer film, glass, ceramic and combination of the same;
    (c) non-woven veil composed of randomly arranged thermoplastic fibers and hardening particles dispersed in the veil, in which the particles are made of a material selected from: PAEK polymers, glass, ceramics and a combination thereof;
    (d) hardening particles comprising a material selected from: PAEK polymers, glass, ceramics and a combination thereof, wherein the hardening particles have a particle size greater than 3 gm;
    (e) metallic mesh, or particles made of a metallic material, selected from: aluminum, copper, titanium, nickel, stainless steel and combination thereof, in which the particles have a particle size greater than 3μιιι.
    Petition 870190132519, of 12/12/2019, p. 29/44
    [2]
    2/5
    2. Thermoplastic laminated compound according to claim 1, characterized by the fact that the matrix thermoplastic resin in the structural layer comprises PAEK ..
    [3]
    3. Laminated thermoplastic compound according to claim 1 or 2, characterized by the fact that the reinforced fibers are made of a material selected from the group consisting of carbon, graphite and glass.
    [4]
    4. Thermoplastic laminated compound according to any one of claims 1 to 3, characterized in that the reinforced fibers in the structural layers are unidirectionally aligned fibers.
    [5]
    Thermoplastic laminated compound according to any one of claims 1 to 4, characterized in that the PAEK polymers of the hardening particles (d) are selected from: polyether ketone (PEK), polyetheretherketone (PEEK), polyether ketone ketone (PEKK) and polyethercetone and etercetonacetone (PEKEKK).
    [6]
    6. Thermoplastic laminated compound according to claim 1, characterized in that the hardening material is a PAEK thermoplastic film (b) or a non-woven web (c) comprising particles of different PAEK polymers or particles made from a mixture glass and PAEK polymer.
    [7]
    7. Thermoplastic laminated compound according to any one of claims 1 to 4, characterized in that the hardening material is a PAEK polymer film containing PAEK particles dispersed therein, in which the particles are made of PAEK polymers with a temperature of melting higher than the melting temperature of the PAEK polymer film.
    [8]
    8. Thermoplastic laminated compound according to any one of claims 1 to 7, characterized in that the content of the hardening material is up to 20% by weight, based on weight
    Petition 870190132519, of 12/12/2019, p. 30/44
    3/5 total matrix resin in the laminate.
    [9]
    A laminated thermoplastic compound according to any one of claims 1 to 4, characterized in that the hardening material is a fiberglass cloth.
    [10]
    10. Compound structure characterized by the fact that it is produced by the consolidation of the laminated thermoplastic compound, as defined in any one of claims 1 to 9.
    [11]
    11. Compound structure, characterized by the fact that it comprises:
    a structural layer composed of reinforced fibers impregnated with a matrix thermoplastic resin; and two hardening layers positioned on opposite surfaces of the structural layer, each of said hardening layers comprising a hardening material selected from:
    (a) non-woven or woven carpet comprising glass fibers or carbon fibers;
    (b) polyarylethylketone polymer film (PAEK) with hardening particles dispersed in it, where the particles are made of a material selected from: PAEK polymers that are different from the PAEK polymer of the PAEK polymer film, glass, ceramic and combination of the same;
    (c) non-woven web comprising thermoplastic fibers randomly arranged, and hardening particles dispersed in the web, in which the particles are made of a material selected from: PAEK polymers, glass, ceramics and a combination thereof;
    (d) hardening particles composed of a material selected from: PAEK polymers, glass, ceramics and a combination thereof, where the hardening particles have a particle size
    Petition 870190132519, of 12/12/2019, p. 31/44
    4/5 greater than 3pm.
    [12]
    Compound structure according to claim 11, characterized by the fact that the thermoplastic matrix resin in the structural layer comprises PAEK.
    [13]
    Compound structure according to claim 11 or 12, characterized in that the hardening material is a PAEK polymer film or a non-woven web composed of hardening particles dispersed therein, in which the particles are made of different PAEK polymers or a mixture of glass and PAEK polymer.
    [14]
    Composite structure according to claim 11 or 12, characterized in that the hardening material is a glass fiber cloth.
    [15]
    Composite structure according to any one of claims 11 to 14, characterized in that the fibers reinforced in the structural layer have a tensile strength greater than 3500 MPa.
    [16]
    Composite structure according to any one of claims 11 to 15, characterized in that the index of the reinforced fibers in the structural layer is at least 55% by weight based on the total weight of the structural layer.
    [17]
    17. Composite structure according to any one of claims 11 to 16, characterized in that the reinforced fibers are made of a material selected from the group consisting of carbon, graphite and glass.
    [18]
    18. Laminate compound produced by the imposition of a plurality of composite structures, according to any one of claims 11 to 17, characterized by the fact that an interlaminar region is formed between two adjacent structural layers and that interlaminar region comprises the hardening material.
    [19]
    19. Thermoplastic laminated compound according to
    Petition 870190132519, of 12/12/2019, p. 32/44
    5/5 claim 1, characterized by the fact that the hardening material is a mixture of different PAEK particles having different melting temperatures.
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    法律状态:
    2018-03-27| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-09-17| B06U| Preliminary requirement: requests with searches performed by other patent offices: suspension of the patent application procedure|
    2020-02-11| B09A| Decision: intention to grant|
    2020-02-18| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 01/08/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
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    US201161528561P| true| 2011-08-29|2011-08-29|
    US61/528561|2011-08-29|
    PCT/US2012/049152|WO2013032620A1|2011-08-29|2012-08-01|Interlaminar toughening of thermoplastics|
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