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    • 专利摘要:
    preform, and, methods for fabrication of a composite structure and for fabrication of dry fibrous tape for automated tape deposition a dry fibrous tape for use in an automated placement process such as atl or afp and a preform produced from of the same. the preform is configured for resin infusion. the tape contains a layer of unidirectional fibers, at least one non-woven film bonded to one side of the fiber layer, and at least binding materials present within the tape. the preform produced from the deposition of this tape exhibits a low volume property which is close to the final thickness of the cured fiber reinforced resin article and no further consolidation or compaction is required.
    公开号:BR112016030776B1
    申请号:R112016030776-3
    申请日:2015-06-25
    公开日:2021-06-29
    发明作者:Robert Blackburn；Samuel Jestyn Hill；Dominique Ponsolle；Carmelo Luca Restuccia
    申请人:Cytec Industries Inc.；
    IPC主号:
    专利说明:

    FUNDAMENTALS
    [001] Three-dimensional polymer composite parts can be manufactured using different methods, one of which is liquid molding. Resin Transfer Molding (RTM) and VARTM are examples of manufacturing processes that involve injecting a liquid resin into a fibrous preform. During the RTM process, the preform is placed in a closed mold cavity, and the resin is injected into the cavity under pressure. The mold with the preform is often placed under vacuum so that the vacuum removes all the air trapped in the preform and speeds up the RTM process. Once the liquid resin fills the mold cavity, the resin is cured, resulting in the formation of a composite part. VARTM is similar to RTM, except that a single-sided tool is typically used with vacuum bagging, and the vacuum pulls the liquid resin into the preform. These techniques are well suited for manufacturing parts of very complex shapes, in many cases at reasonable production rates. Fiber architecture, preform permeability and fabric crimps, resin viscosity and operating temperature all have an influence on fabric wetting.
    [002] To prepare the preform, the dry layers of unidirectional reinforcing fibers or woven fabrics are deposited in a similar way to the way resin-impregnated prepregs are deposited. It would be desirable to employ Automated Tape Deposition (ATL) and Automated Fiber Placement (AFP) for preform deposition to reduce costs. However, the technological challenges connected with manufacturing narrow-width dry fiber products suitable for automated placement processes such as ATL and AFP require further development. SUMMARY
    [003] Described herein is a dry, flat tape for use in manufacturing a fibrous preform by an automated placement process such as ATL or AFP. The tape contains a unidirectional fiber layer, at least one non-woven film bonded to one side of the fiber layer, and at least one binding material present within the tape. The preform produced from the deposition of a plurality of such tape exhibits a low volume property which is close to the final thickness of the cured fiber reinforced resin article and further consolidation or compaction is not required. BRIEF DESCRIPTION OF THE DRAWINGS
    [004] Fig. 1 is a partial view of a dry tape where the outer thermoplastic film holds the outer fibers together, but the inner dry fibers are free to move.
    [005] Fig. 2 schematically illustrates a binder treated unidirectional tape with a single non-woven film bonded to one side in accordance with an embodiment of the present description.
    [006] Fig. 3 schematically illustrates a unidirectional tape treated with binder with non-woven films bonded to opposite sides according to another embodiment of the present description. DETAILED DESCRIPTION
    [007] In the manufacture of fiber-reinforced polymer composites, dry fiber materials offer the user an increased level of control and manipulation in the positioning and orientation of fibers due to the inherent lack of resin when compared to pre-impregnated materials that have been impregnated with a resin. However, without the ability to secure the fibers to their desired position, significant problems in preform quality and consistency can be expected. This is particularly prevalent in situations where the preforms require manipulation to be combined into a dry assembly of a master preform for subsequent infusion or where the preforms require other post-consolidation operations such as near-shape trimming. definitive. There are significant challenges in using dry fiber materials for preform deposition if poor compaction behavior of the fiber materials is observed causing a significant increase in preform volume and loose preform materials. Consequently, the subsequent manipulation of the preform becomes more difficult because there is a risk that the layers will separate, while the excess volume will cause the preforms to be oversized presenting a difficulty to fit appropriate tools and can cause impediments to performance to the final composite due to a low fiber to resin ratio after injection and curing.
    [008] This excess volume has been reported by composite material manufacturers in which the preforms have incorporated a thermoplastic intercalation film. It also predominantly imposes preforms with a thickness greater than 4 mm.
    [009] One solution to the above matter is to provide a dry tape configuration where a non-woven thermoplastic film is laminated to each face of a unidirectional fiber tow in order to encapsulate the tape and to allow a medium for the fiber tow be held in place with heat and pressure. However, it has been found that dry tapes constructed in this manner typically exhibit poor thickness control in the presence of thickness and volume variability. Fig. 1 shows the loose fiber matter related to this type of tape - the thermoplastic film holds the outer fibers together, but the dry inner fibers are free to move.
    [0010] The present description provides a solution to the increased thickness/volume matter associated with conventional and unidirectional dry fiber tapes. One aspect of the present description is to provide a dry fiber tape configuration to be used in an automated placement whereby the preform produced by deposition of the tapes exhibits a low volume property which is close to the final thickness of the reinforced resin article with cured fibers and no further consolidation or compaction is required.
    [0011] One aspect of the present description relates to a flat dry tape which includes a layer of unidirectional fibers aligned parallel to each other, a non-woven film bonded to at least one side of the unidirectional fiber layer, a first material of binders (also referred to herein as "binder") distributed on either side of the unidirectional fiber layer and penetrated through portions of the non-woven film, or distributed throughout the tape, including in the spaces between the unidirectional fibers and in portions of the film.
    [0012] According to another embodiment, a first binder is distributed on each side of the unidirectional fiber layer and penetrated through portions of the non-woven film, and a second binder (different from the first binder) is distributed throughout the tape, including in the spaces between the unidirectional fibers and in portions of the film.
    [0013] In some embodiments, two non-woven films of thermoplastic fibers are attached to opposite sides of the unidirectional fiber layer.
    [0014] According to an embodiment, the non-woven film comprises fibers which may include thermoplastic fibers and/or carbon fibers. These fibers can be oriented randomly or not depending on the conditions of the film manufacturing process. Fiber length can range from 1/8 inches (0.32 cm) to 2 inches (5.08 cm) in length. The areal weight of the non-woven film in this modality is preferably less than 10 grams per square meter (gsm).
    [0015] According to another embodiment, the non-woven film is in the form of a thermoplastic grid. Thermoplastic grids can be manufactured by extruding a thermoplastic material to form an engineered orientation network or controlled pattern in which the thermoplastic material is deposited. These orientations can be 0/± 60, for example, within the same grid. A supplier of this type of network is Protechnic (France). The thermoplastic grid described herein may have an areal weight in the range of 2-50 gsm, preferably 2-20 gsm, more preferably 2-10 gsm.
    [0016] According to another embodiment, the non-woven film is in the form of a porous thermoplastic membrane with a controlled pattern of openings. As examples, the porous membrane can be formed by mechanically perforating a continuous thermoplastic film or formed by conventional molding processes. Such a membrane may comprise a plurality of micrometer-sized openings of varying shapes so as to provide an open, liquid-permeable structure. The shape and density of the openings can be adapted to provide the desired physical characteristics. More specifically, the openings are configured to allow the resin flow used in the subsequent resin infusion to pass through. Porous membrane openings can take a variety of shapes. Non-limiting examples include holes/openings with cross sections that are circular, oval, square, triangular, hexagonal, etc. More than one pattern can be present on a membrane. The porous membrane described herein may have an areal weight in the range of 2-50 gsm, preferably 2-20 gsm, more preferably 2-10 gsm. In some embodiments, the non-woven film is composed of carbon fibers. In other embodiments, the non-woven film is composed of one or more types of thermoplastic fibers. Alternatively, the film can contain a hybrid mixture of inorganic fibers and polymeric fibers. For non-woven films in the form of thermoplastic fibers or porous membrane, the thermoplastic material can be selected from polyamides, thermoplastic polyamides, aliphatic polyamides, cycloaliphatic polyamides, polyphthalamides, polyamidoimides, aromatic polyamides, polyimides, polyetherimides, polyesters, polyurethane phenyleneoxides thermoplastics, polyacetals, polyolefins, thermoplastic polyolefins, polyethersulfones, polyetherethersulfones, polysulfones, polyphenylene sulfone, polyether-etherketones, polyetherketone ketone, thermoplastic polyimides of poly(phenylenesulfide), liquid crystal polymers (LCP), phenoxys, acrylics, acrylates copolymers thereof.
    [0017] The opening of the non-woven film (whether in the form of random fibers, grid or porous membrane) is important to facilitate the removal of air and resin flow during the resin injection or infusion process.
    [0018] Neither the first binder nor the second binder discussed above form a continuous layer. If the binders form a continuous film on the surface of the dry tape, this can prevent the resin from satisfactorily penetrating through the thickness of the preform during the resin injection cycle of liquid molding processes such as RTM or VARTM. As such, the tape is porous and permeable to liquid resins to be used in liquid molding.
    [0019] The total content of binder materials in the dry tape is about 15% or less by weight, e.g. 0.1 and 15% by weight, based on the total weight of the dry sliver, and the structural fibers are the main component of the fibrous material, for example greater than 80% by weight based on the total weight of the dry sliver.
    [0020] The tapes described here can have a width of up to 1.3 m (50 inches). According to an embodiment, each tape has a width of 0.1 cm to 61 cm, a length that is at least 10 times its width and a thickness of approximately 75 µm to 300 µm, including 100 µm to 250 µm.
    [0021] According to an embodiment, the method for manufacturing the dry tape includes: applying the first binding material, in particulate form, to a continuous sheet of dry fibers of unidirectional and high strength fibers (e.g., fibers of carbon); bonding a non-woven film (e.g., carbon fibers or thermoplastic fibers) to at least one side of the fiber web; applying a second binding material, in the form of a liquid composition, to the unidirectional fiber/film laminate, e.g., dip coating; and drying the binder treated laminate in an oven. The first binding material can be in particulate form when it is applied to unidirectional fibers. In an alternative embodiment, particles of the first binder material are applied to the non-woven film and the film is then bonded to the fiber web. The dry binder treated laminate is then strip-cut into narrow-width tapes that are suitable for ATL/AFP and, optionally, the strip-cut tapes are wound onto spools.
    [0022] According to another embodiment, the method for manufacturing the dry tape includes: applying the first binding material, in a liquid form, to a continuous sheet of dry fibers of high strength unidirectional fibers, such as carbon fibers, for example, by dip coating or spray coating; and drying the binder treated unidirectional fibers in an oven; bonding a non-woven film (e.g., carbon fibers or thermoplastic fibers) to at least one side of the fiber web; applying a second binding material, in the form of a liquid composition, to the unidirectional fiber/film laminate, for example, by dip coating or spray coating; and drying the binder treated laminate in an oven. The first binding material can be in the form of an aqueous emulsion when applied to unidirectional fibers. In an alternative embodiment, the first binder material is used in making or applied to the non-woven film, and the film is then bonded to the fiber web. The dry binder treated laminate is then strip-cut into narrow-width tapes that are suitable for ATL/AFP and, optionally, the strip-cut tapes are wound onto spools.
    [0023] According to yet another modality, the first and second binders were combined into a binder, in a liquid form. Then, the method for manufacturing the dry tape includes: applying the combined binders, in a liquid form, to a dry fiber sheet of high strength unidirectional fibers, for example, such as carbon fibers, for example, by dip or spray coating; and drying the binder treated unidirectional fibers in an oven; bonding a non-woven film (eg carbon fibers or thermoplastic fibers) to at least one side of the fiber web. The dry binder treated laminate is then cut into narrow width tapes which are suitable for ATL/AFP and optionally the strip cut tapes are wound onto spools.
    [0024] A preform for use in a liquid molding process can be prepared by depositing a plurality of dry tapes through an automated placement process such as ATL or AFP. A volume test is designed to determine the effect of tape on volume. It was found that when the preform is heated to a temperature of 165°C for 30 seconds, the preform exhibits a low volume property whereby the thickness of the preform (T2) after heating is reduced from 1% to 15% in relation to the initial thickness of the T1 preform (or T2 = 0.85 T1 to 0.99 T1).
    [0025] The preform described above can be used in the fabrication of a composite structure. The method for composite fabrication may include: a) depositing a plurality of the aforementioned dry tapes by an automated placing process (ATL or AFP) to form a multilayer preform, wherein the consolidated preform has an initial thickness T1; b) infusing the preform with a liquid resin in a liquid molding process; c) curing the resin-infused preform to form a composite structure having a thickness T2.
    [0026] The preform exhibits a low volume property on heating, as determined by the heating and forming process of the automated placement process, and the cured thickness of the composite structure, T2, is reduced from 0% to 10% of the thickness of preform T1 (or 0.90 T1 < T2 < 1.00 Ti), and no further consolidation is required after the tape deposition process.
    [0027] Pre-compaction of the preform before curing is minimal (or not necessary) because pre-compaction occurs during the ATL/AFP process as tapes containing binders are being deposited to form the pre- form.
    [0028] In one embodiment, the first binding material is a solid at a temperature of up to 50°C), has a softening point at a temperature in the range of 65°C to 125°C and comprises a combination of epoxy resin and thermoplastic polymer, but is devoid of any catalyst or crosslinking agent that is active above 65°C. The thermoplastic polymer in the first binder material may be a polyarylsulfone polymer comprising ether linked repeating units and optionally thioether linked repeating units, the units being selected from: -(Ph-A-Ph) - and optionally -(Ph) )a - where A is CO or SO2, Ph is phenylene, n = 1 to 2 and may be fractional, a = 1 to 4 and may be fractional, provided that when a is greater than 1, the phenylenes are linearly linked through of a single chemical bond or a divalent group other than -CO- or -SO2-, or are fused together directly or through a cyclic moiety selected from the group consisting of an acidic alkyl group, a (hetero)aromatic, a cyclic ketone , a cyclic amide, an imide, a cyclic imine and combinations thereof. In one embodiment, the thermoplastic polymer is a PES-PEES copolymer. The method for making this solid binding material can be found in U.S. Patent No. 8,927,662, issued to Cytec Technology Corp., the contents of which are incorporated herein by reference.
    [0029] According to another embodiment, the first binding material is an aqueous binder dispersion containing (a) one or more multifunctional epoxy resins, (b) at least one thermoplastic polymer, (c) one or more surfactants selected from surfactants anionic and nonionic surfactants, d) water and preferably is essentially free of organic solvents. Optional additives such as organic or inorganic fillers and a defoamer can also be included in the binder composition.
    [0030] The thermoplastic polymer in this embodiment is soluble in a thermoset matrix resin after curing the matrix resin. An example is a polyaryl sulfone comprised of ether linked repeating units and optionally thioether linked repeating units as discussed above.
    The polyarylsulfone may contain repeating units of -(PhSO2Ph) -, wherein the -(PhSO2Ph) unit is present in the polyarylsulfone in such a proportion that, on average, at least two of said -(PhSO2Ph)n- units are in sequence on each polymer chain present.
    [0032] Preferably, the polyarylsulfone is a copolymer containing the following units:
    where X is O or S and may differ from unit to unit, and a is 1-4.
    [0033] The thermoplastic polymer can have a molecular weight in the range of 2,000 to 30,000, measured by high pressure size exclusion chromatography (HPSEC) and a glass transition temperature (Tg) greater than 150°C measured by Differential Scanning Calorimetry (DSC).
    [0034] The one or more surfactants in this embodiment is(are) selected from: a) nonionic surfactant which is a mono- or multifunctional block or graft block copolymers comprising hydrophilic and hydrophobic blocks; b) anionic surfactant which is represented by the following formula: A—R where R is an alkyl, aryl, aryl-alkyl, or alkylene chain having 4-50 carbon atoms (C4 to C50); and A is lithium, sodium, potassium, ammonium, quaternary ammonium salt of a carboxylic, sulfonic or phosphoric acid group; and c) a combination of nonionic surfactant and anionic surfactant.
    [0035] The nonionic surfactant includes a backbone portion and the hydrophobic and hydrophilic blocks form part of the backbone or protrude substantially from the backbone portion to form grafts, or a combination thereof.
    [0036] Preferably, the nonionic surfactant is selected from the following compounds: (a) polyoxamer represented by the following formula:
    where x, y, z = whole numbers or fractions provided that the ratio of (x + z) to y is 1.32 or greater and the ethylene oxide content is in the range of 50% to 99% by weight, and wherein the polyoxamer has a number average molecular weight (Mn) in the range 1,000 g/mol-100,000 g/mol as measured by gel permeation chromatography (GPC); and
    where a, b, c, d, e, f, g, h are whole numbers or fractions, and the polyoxamine has a number average molecular weight in the range 1,000 g/mol -100,000 g/mol.
    [0037] The liquid binder composition discussed above may further include a crosslinking agent selected from aminoplasts, phenolics, azlactones, aziridines and block isocyanates. The binder composition is a polymeric emulsion with a solids content of 40% to 70% and particle size distribution in the range of 50 nm to 10000 nm. The particle size distribution can be determined by dynamic light scattering. The method for preparing this liquid binder composition can be found in U.S. Pub. No. 2014/0179187, granted to Cytec Technology Corp., the contents of which are incorporated herein by reference.
    [0038] A liquid binder composition, such as polymer emulsion, is applied to coat and infiltrate the fibers in the tape. The water is then evaporated according to a controlled time/temperature profile to achieve the desired balance of physical properties. The liquid binder composition is applied so that it penetrates through the resulting tape structure.
    [0039] In embodiments where two different binding materials are applied, the first binding material is as described above and the second binding material may be a partially or fully crosslinked copolymer of polyhydroxyether and polyurethane. During dry tape manufacturing, the second binding material can be applied as a liquid binder composition that is based on a water-based dispersion containing: (i) a polyhydroxyether and polyurethane copolymer, (ii) an agent crosslinking; and optionally, (iii) a catalyst. The crosslinking agent can be an aminoplast crosslinking agent, for example, a methoxyalkyl melamine class of aminoplast crosslinking agents. The catalyst may include, but is not limited to, proton donor acids such as carboxylic, phosphoric, acid alkyl, sulfonic, disulfonic and/or Lewis acid phosphates such as aluminum chloride, bromide or halide, ferric halide, tri boron halides, and many others in both categories as is well known to one skilled in the art.
    [0040] According to another embodiment, the second binding material is a polyurethane or a modified polyurethane polymer. During dry tape manufacturing, the second binder material can be applied as a liquid binder composition that is based on a water-based dispersion containing: (i) a polyurethane; and (ii) optionally, a cross-linking agent. As such, the fabricated tape may contain an uncrosslinked, partially or fully crosslinked polyurethane polymer.
    [0041] Polyurethane can be synthesized by reacting a polyisocyanate with one or more polyols having a number average molar mass (Mn) of at least 400 g/mol (measured by GPC), selected from a group consisting of polyether polyols and aliphatic or aromatic polyester polyols and optionally: a compound capable of forming anions and having at least two groups that are reactive towards isocyanate groups; a low molar mass polyol with Mn from 60 to 400 g/mol; a combination of them.
    [0042] Suitable polyisocyanates (which means compounds having a plurality of isocyanate groups) for preparing the polyurethane include any organic polyisocyanate, preferably monomeric diisocyanates. Especially preferred are polyisocyanates, especially diisocyanates, with aliphatically and/or cycloaliphatically bonded isocyanate groups, although they are not excluded and polyisocyanates having aromatically bonded isocyanate groups can also be used.
    [0043] Examples of suitable polyisocyanates that can be used include ethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,4,4-trimethyl-1,6-hexamethylene diisocyanate, 1, 12-dodecane diisocyanate, cyclobutane-1,3-diisocyanate, cyclohexane-1,3- and/or -1,4-diisocyanate, 1-isocyanato-2-isocyanatomethyl cyclopentane, 1-isocyanate-3,3,5-trimethyl -5-isocyanatomethyl cyclohexane (isophorone diisocyanate or IPDI), 2,4- and 2,6-hexahydrotolylene diisocyanate, 2,4'- and/or 4,4'-dicyclohexylmethane diisocyanate, a,a ,a',a-tetramethyl-1,3- and/or 1,4-xylylene diisocyanate, 1,3- and 1,4-xylylene diisocyanate, 1-isocyanato-1-methyl-4(3)-isocyanatomethylcyclohexane , 1,3- and 1,4-phenylene diisocyanate, 2,4- and/or 2,6-tolylene diisocyanate, diphenyl methane-2,4'- and/or -4,4'-diisocyanate, naphthalene-1, 5-diisocyanate, triphenylmethane-4.4',4"- triisocyanate, polyphenyl polymethylene polyisocyanates of the type obtained by condensation of aniline with formaldehyde followed by phosge nation and mixtures of the aforementioned polyisocyanates.
    Suitable polyols preferably have a number average molar mass (Mn) of 400 g/mol to 5000 g/mol. Examples of suitable polyols include aliphatic polyether polyols such as polyoxyethylene glycol, polyoxypropylene glycol, or mixed polymers of such units, polyester polyols obtained by polycondensation of diols or polyols with dicarboxylic or polycarboxylic acids, such polyester polyols including polyethylene adipate, mixed polyesters derivatives of ethylene glycol, hexane diol, trimethylol propane, adipic and terephthalic acid, etc. Other building blocks that can constitute or be included in these polyester polyols are hydroxycarboxylic acids such as hydroxybutyric acid or hydroxycaproic acid or their lactones.
    [0045] Suitable aromatic polyether polyols are epoxy resins or phenoxy resins, or mixtures thereof.
    [0046] Examples of compounds capable of forming anions include polyols, particularly diols and polyamines, particularly diamines, or hydroxyamines, which carry 1 to 3 carboxylic or sulfonic acid groups per molecule.
    [0047] Examples of compounds capable of forming anions include polyols, particularly diols and polyamines, particularly diamines, or hydroxyamines, which carry 1 to 3 carboxylic or sulfonic acid groups per molecule.
    [0048] Examples of carboxylate-containing compounds of this composition include the reaction of isocyanate-terminated polyol prepolymers (obtained by reacting excess diisocyanate with hydroxyl-containing prepolymers) with hydroxyl-containing carboxylic acids. Examples of the cationic terminated compounds of this invention include the quaternary ammonium or phosphonium prepolymers. Such cationic compositions can be prepared by reacting tert-amine containing alcohols with the aforementioned isocyanate terminated prepolymers, followed by reaction with a quarternizing agent such as dimethyl sulfate or an alkyl halide as is known to one skilled in the art . Examples of low molar mass polyols with a molar mass preferably from 60 to 400 include ethylene glycol, diethylene glycol, 1,4-butanediol, cyclohexanediol and any other diol known to those skilled in the art.
    Suitable crosslinkers for polyurethanes may include, but are not limited to, diisocyanate or polyisocyanate crosslinkers, for example an aliphatic or aromatic polyisocyanate crosslinker.
    [0050] Examples of polyisocyanate crosslinking agents are modified aliphatic polyisocyanates marketed under the tradename Perapret Booster XLR by BASF or the tradename Desmodur® N by Bayer. Examples of aromatic polyisocyanate are polyisocyanate based on toluene diisocyanate (TDI) marketed by Bayer under the trade name Desmodur® L.
    [0051] In yet another embodiment, the second binding material includes an epoxy resin or a modified epoxy resin.
    [0052] During dry tape manufacturing, the second binding material can be applied as a liquid binder composition that is based on a water-based dispersion containing: (i) an epoxy resin; and (ii) optionally, a cross-linking agent. As such, the fabricated tape may contain an uncrosslinked, partially or fully crosslinked epoxy resin.
    [0053] Examples of epoxy resins are those that have at least two epoxide groups per molecule and preferably have a polyether structure which in turn has portions derived from 1, 2, 3-trihydroxypropane and portions derived from dihydroxy or poly compounds. -hydroxy aromatics. Polyepoxides generally have, on average, at least two epoxy groups per molecule. Said epoxy compounds may be aliphatic, cycloaliphatic, aromatic or heterocyclic and may also contain hydroxyl groups.
    [0054] Preferably, these epoxy compounds are polyglycidyl ethers based on polyhydric alcohols, preferably dihydric, polyhydric phenols, preferably dihydric, hydrogenation products of said phenols, novolacs and/or aniline.
    As polyhydric phenols, they may include, for example, resorcinol, hydroquinone, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), isomeric mixtures of dihydroxydiphenylmethane (bisphenol F), tetrabromobisphenol A, 4, 4'-dihydroxydiphenylcyclohexane, 4,4'-dihydroxy-3,3'-dimethyldiphenylpropane, 4,4'-dihydroxydiphenyl, 4,4'-dihydroxybenzophenone, bis(4-hydroxyphenyl)-1,1- ethane, bis(4-hydroxyphenyl)-1,1-isobutane, bis(4-hydroxy-tert-butylphenyl)-2,2-propane, bis(2-hydroxynaphthyl)methane, 1,S-dihydroxynaphthalene, tris(4- hydroxyphenyl)hydroxyphenyl)ether, and bis(4-hydroxyphenyl)sulfone, and also the chlorination and bromination products of the aforementioned compounds. Bisphenol A is particularly preferred.
    Polyglycidyl ethers of polyhydric alcohols are also suitable as epoxy resins. As examples of such polyhydric alcohols, they may include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, polyoxypropylene glycols (with two to ten 1,2-propyleneoxy units), 1,3-propylene glycol, 1,4-butylene glycol, 1,S-pentanediol, 1,6-hexanediol, 1,2,6-hexanetriol, glycerol and bis(4-hydroxycyclohexyl)-2,2-propane.
    Suitable resins also include aromatic glycidylamine epoxy resins such as aromatic polyamine condensates such as aniline, diaminodiphenylmethane, o-, p-, m-aminophen1,2-amino-p-cresol, 6-amino-p-cresol, o-, p-, m-xylylenediamine, o-, m-, p-chloroaniline, o-, m-, p-bromoaniline, o-, m-, p-iodoaniline, bisaminomethylcyclohexane with epichlorohydrin.
    [0058] It is also possible to use polyglycidyl esters of polycarboxylic acids that are obtained by a reaction of similar epichlorohydrin or epoxy compounds with an aliphatic, cycloaliphatic or aromatic acid, such as oxalic acid, succinic acid, adipic acid, glutaric acid, acid phthalic acid, terephthalic acid, hexahydrophoric acid, 2,6-naphthalenedicarboxylic acid and dimerized linolenic acid. Examples are diglycidyl adipate, diglycidyl phthalate and diglycidyl hexahydrophthalate, epoxy ester resins such as copolymers of glycidyl (meth)acrylate with an ethylenically unsaturated monomer, for example, acrylonitrile, hydroxy(meth)acrylate, (met) N,N'-dimethylaminoethyl acrylate; epoxy resins such as epoxidized soybean oil. A detailed enumeration of suitable epoxy compounds can be found on pages 1-1 to 3-20 of Henry's Handbook of Epoxy Resins published by McGraw-Hill Brook Company in 1967, and in Lee and Neville's "Handbook of Epoxy Resins", 1967, Chapter 2. Mixtures of the various epoxy compounds mentioned are also contemplated.
    Suitable crosslinking agents for epoxy resins may include, but are not limited to, amino compounds having a molecular weight of up to 500 per amino group, for example an aromatic amine or a guanidine derivative. 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'-methylene-bis(2,6-diethyl)-aniline (MDEA, Lonza); 4,4'-methylenebis-(3-chloro, 2,6-diethyl)-aniline (MCDEA; Lonza); 4,4'-methylene-bis(2,6-diisopropyl)-aniline (M-DIPA; Lonza); 3,5-diethyl toluene-2,4/2,6-diamine (D-ETDA 80; Lonza); 4,4'-methylene-bis(2-isopropyl-6-methyl)-aniline (M-MIPA; Lonza); 4-chlorophenyl-N,N-dimethyl-urea (for example Monuron); 3,4-dichlorophenyl-N,N-dimethyl-urea (e.g. Diuron™) and dicandiamide (Amicure™ CG 1200, Pacific Anchor Chemical). Bisphenol chain extenders, such as bisphenol-S or thiodiphenol, are also useful as curing agents for epoxy resins. Suitable curing agents also include: i) anhydrides, particularly polycarboxylic anhydrides, such as nadic anhydride, methylnadic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride or trimethylic anhydride; ii) amino resin crosslinking agents such as methylated and butylated melamines, mixed and alkylated imino ether melamines, alkylated ureas, benzoguanamines and glycouryls; iii) phenolics; iv) azlactones; and v) aziridines.
    [0060] One or more catalyst(s) may also be used to accelerate the cure reaction. Suitable catalysts are well known in the art and include strong acids such as super acids and block versions thereof, Lewis acids or bases. Specific examples include compositions comprising boron trifluoride, such as the etherates or their amine adducts (for example, the boron trifluoride ethylamine adduct), particularly where epoxy resin precursors are used in conjunction with the amine curing agents above mentioned.
    [0061] In yet another embodiment, the second binding material includes a polyhydroxyether or "phenoxy" resin. During dry tape manufacturing, the second binder material can be applied as a liquid binder composition that is based on a water-based dispersion containing: (i) a phenoxy resin; and (ii) optionally, a cross-linking agent. Thus, the fabricated tape may contain an uncrosslinked, partially or fully crosslinked phenoxy resin.
    [0062] The poly(hydroxyether) resin has the general formula:
    wherein D is the radical residue of a dihydric phenol, E is a hydroxyl-containing radical residue of an epoxide and n represents the degree of polymerization and is at least 30 and is preferably 80 or more. The term "thermoplastic poly(hydroxy ether)" is intended to include mixtures of at least two thermoplastic poly(hydroxy ethers).
    [0063] The dihydric phenol contributing the residue of the phenol radical, D, may be a mononuclear dihydric phenol or a dihydric polynuclear phenol, such as those having the general formula:
    where Ar is a divalent aromatic hydrocarbon such as naphthylene and preferably phenylene, X and Y which may be the same or different are alkyl radicals, preferably having 1 to 4 carbon atoms, halogen atoms, i.e. fluorine, chlorine , bromine and iodine or alkoxy preferably having 1 to 4 carbon atoms, a and b are integers having a value from 0 to a maximum value corresponding to the number of hydrogen atoms in the aromatic radical (Ar) which may be substituted by substituents and R is a bond between adjacent carbon atoms as in dihydroxydiphenyl or is a divalent radical including, for example,
    and divalent hydrocarbon radicals such as alkylene, alkylidene and cycloaliphatic, for example, cycloalkylidene, halogenated alkoxy or aryloxy, alkylidene and cycloaliphatic substituted alkylene radicals as well as alkarylene and amomatic radicals including substituted alkyl, alkoxy or aryloxy and a ring fused with an Ar group; or R can be polyalkoxy or polysiloxy, or two or more alkylidene radicals separated by an aromatic ring, a tertiary amino group, an ether bond, a carbonyl group or a sulfur-containing group such as sulfoxide and the like.
    [0064] Examples of specific dihydric polynuclear phenols include, but are not limited to: bis(hydroxyphenyl)alkanes such as 2,2-bis-(4-hydroxyphenol)propane, 2,4'-dihydroxydiphenylmethane, bis(2-hydroxyphenyl) methane, bis(4-hydroxyphenyl)methane, bis(4-hydroxy-2,6-dimethyl-3-methoxyphenyl) methane, 1,1-bis(4-hydroxyphenylethane, 1,2-bis(4-hydroxyphenyl)-ethane , 1,1-bis(4-hydroxy-2-chlorophenyl)ethane, 1,1-bis-(3-methyl-4-hydroxyphenyl)ethane, 1,3-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3-phenyl-4-hydroxyphenyl)propane, 2,2-bis(2-isopropyl-4-hydroxyphenyl)propane, 2,2-bis(4-hydroxylnaphthyl)propane, 3,3-bis( 4-hydroxylnaphthyl)pentane, 2,2-bis(4-hydroxyphenyl)heptane, bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)cyclohexylmethane, 1,2-bis(4-hydroxyphenyl-1, 2-bis(phenyl)propane, 2,2-bis(4-hydroxyphenyl)-1-phenyl-propane and the like; di(hydroxyphenyl)sulfones such as bis(4-hydroxyphenyl)sulfone, 2,4'- dihydroxydiphenylsulfone, 5'-chloro-2,4'-dihydroxydiphenylsulfone, 5'-chloro-4,4'-dihydroxydiphenylss ulphona and the like; di(hydroxyphenyl) ethers, such as bis(4-hydroxy-phenyl) ether, the 4,3'-, 4,2'-, 2,2'-, 2,3'-, dihydroxydiphenyl ethers, 4, 4'-dihydroxy-2,6-dimethyldiphenyl ether, bis(4-hydroxy-3-isobutylphenyl) ether, bis(4-hydroxy-3-isopropylphenyl) ether, bis(4-hydroxy-3-chlorophenyl) ether, bis( 4-hydroxy-3-fluorophenyl)ether, bis(4-hydroxynaphthyl)ether, bis(4-hydroxy-3-chloronaphthyl)ether, bis(2-hydroxydiphenyl)ether, 4,4'-dihydroxy-2,5-dimethoxydiphenyl ether, 4,4-dihydroxy-2,5-diethoxydiphenyl ether, and the like.
    Alternative suitable dihydric polynuclear phenols are the reaction products of 4-vinylcyclohexene bisphenol and phenols, eg 1,3-bis(p-hydroxyphenyl)-1-ethylcyclohexane and the products of reaction of dipentene bis-phenol or its isomers and phenols such as 1,2-bis(p-hydroxyphenyl)-1-methyl-4-isopropylcyclohexane as well as bisphenols such as 1,3,3'-trimethyl-1 -(4-hydroxyphenyl)-6-hydroxy-indane and 2,4-bis(4-hydroxyphenyl)-4-methylpentane, and the like.
    wherein X and Y are as defined above, a and b have values from 0 to 4, inclusive, and R is a divalent saturated aliphatic hydrocarbon radical, particularly, alkylene and alkylidene radicals having 1 to 3 carbon atoms and cycloalkylene radicals having up to and including 10 carbon atoms.
    Mixtures of dihydric phenols may also be used, and whenever the term "dihydric phenol" or "polynuclear dihydric phenol" is used herein, mixtures of these compounds are intended to be included.
    [0067] The epoxide that contributes to the hydroxyl-containing radical residue, and, can be monoepoxide or diepoxide. A monoepoxide contains such an oxirane group and provides an E radical residue containing a single hydroxyl group, a diepoxide contains two such oxirane groups and provides an E radical residue containing two hydroxyl groups. Saturated epoxides, by which the term means diepoxides free from ethylenic unsaturation, i.e., >C-C< and acetylenic unsaturation, i.e., -C=C- are preferred. Particularly preferred are saturated halogen substituted monoepoxides, i.e., saturated epichlorohydrins and diepoxides which contain only carbon, hydrogen and oxygen, especially those in which the vicinal or adjacent carbon atoms form a part of an aliphatic hydrocarbon chain. The oxygen in these diepoxides can be, in addition to oxirane oxygen, ether oxygen -0-, oxacarbonyl oxygen, carbonyl oxygen and the like.
    [0068] Specific examples of monoepoxides include epichlorohydrins such as epichlorohydrin, epibromohydrin, 1,2-epoxy-1-methyl-3-chloropropane, 1,2-epoxy-1-butyl-3-chloropropane, 1,2-epoxy-2 -methyl-3-fluoropropane, and the like.
    Illustrative diepoxides include diethylene glycol-bis(3,4-epoxycyclohexane-carboxylate), bis(3,4-epoxycyclohexylmethyl)adipate, bis(3,4-epoxycyclohexylmethyl)phthalate, 6-methyl- 3,4-epoxycyclohexylmethyl-2-chloro-3,4-epoxycyclohexane-carboxylate, diglycidyl ether, bis(2,3-epoxycyclopentyl)-ether, 1,5-pentanediol bis(4-methyl-3,4) -epoxycyclohexylmethyl)ether, bis(2,3-epoxy-2-ethylhexyl)adipate, diglycidyl maleate, diglycidyl phthalate, 3-oxa-tetracyclo[4.4.0.17,10.02.4]-undec-8-yl 2 ,3-epoxypropyl ether, bis(2,3-epoxycyclopentyl)sulfone, bis(3,4-epoxyhexoxypropyl)sulfone, 2,2'-sulfonyldiethyl, bis(2,3-epoxycyclopentanecarboxylate), 3-oxatetracyclo- [4.4.0.17,10.02.4]-undec-8-yl 2,3-epoxybutyrate, 4-pentenal-di-(6-methyl-3,4-epoxycyclohexylmethyl)acetal, ethylene glycol bis(9,10-epoxystearate ), diglycidyl carbonate, bis(2,3-epoxybutylphenyl)-2-ethylhexyl phosphate, diepoxydioxane, and 2,3-dimethylbutadiene dioxide.
    [0070] Examples of preferred water-based phenoxy resin are condensation polymers derived from bisphenol-A (2,2-bis(p-hydroxyphenyl)propane and epichlorohydrin having the structural formula:

    [0071] Examples of suitable crosslinking agents for phenoxy resins include isocyanates, anhydrides, triazines and melamines.
    [0072] Suitable crosslinking agents include aminoplast or amino resin crosslinking agents which are the products of the reaction of urea or melamine with formaldehyde and an alcohol. In addition to urea and melamine, other compounds with similar functionalities can also be used such as benzoguanamines, glycolurils, cyclic ureas, hydantoins, primary and secondary amides, carbamates, etc., when some property advantages are required.
    [0073] The liquid phenoxy-based binder composition discussed above can be applied as a polymer emulsion to coat and infiltrate the fibers in the tape. The water is then evaporated according to a controlled time/temperature profile to achieve the balance of desired physical properties. The liquid binder composition is applied so that it penetrates through the resulting tape structure.
    [0074] Fig. 2 schematically illustrates a dry tape according to an embodiment of the present invention in which a single non-woven film is bonded to one side of a layer of unidirectional fibers (eg carbon fibers). Fig. 3 shows an embodiment in which unidirectional fibers are placed between two non-woven films. The first binding binder remains on the outer surfaces of the tape while the second binder penetrates through the entire thickness of the tape. Each binder has specific benefits. The first binder gives the film bonding to the unidirectional fibers, as well as the cohesion and stability of the tape during its manufacture and allows a very good control of the width of the tape cut into strips. It also allows for an effective deposition process and a preform fabrication process by bonding the strips cut into strips to the previously deposited tool or layers.
    [0075] The second binder holds the unidirectional fiber filaments of the tape together. As a result, it improves the abrasion resistance as well as the resistance to fraying of the strip cut tape, which in turn allows for better control of the width of the strip cut tape. It also increases the stiffness of strip cut tape, resulting in improved handling during the ATL/AFP deposition process. And because the filaments are bonded together, the second bonding material also contributes to the smaller volume of the dry tape and fabricated preforms.
    [0076] When the dry tape contains only thermoplastic films bonded to opposite sides of the unidirectional fiber layer, without any binding materials, a "reverse spring" effect is observed. The bed of dry fibers behaves like a spring, and demonstrates the relaxation of the thickness and the poor overall stability of the preform, particularly in the case of a thick deposition with a thickness greater than 4 mm. This reverse spring effect is negated by the presence of the first and second binding materials.
    [0077] It is also believed that the combination of binders described herein contributes to the low volume of the preform formed by deposition of the dry tapes because they keep the overlapping layers of the preform bonded together.
    [0078] The combination of binders described herein helps to stabilize the unidirectional structural fibers during the tape deposition process to form the preform, but does not interfere with the resin infusion process nor with the mechanical performance of the final composite part. The non-woven film increases resin diffusion in the plane during the resin injection cycle. As an added benefit, the film, which is located in the interlaminar region between structural and highly resin-laden fiber layers, can act as a carrier for materials such as stiffening particles or stiffening fibers to further stiffen the resulting composite.
    [0079] The dry flat tape described here is a self-supporting fibrous material. The term "dry" as used herein refers to a material which can be considered to have a dry feel, which is non-tacky to the touch and substantially free of any matrix resin other than the binders described above. The term "self-supporting" refers to a cohesive form of fibers or filaments that do not separate from one another, for example, during the slitting process and other subsequent manipulations such as when the fibrous product is processed through automated machines. Furthermore, the dry binder treated tape can be stored at room temperature and does not need to be refrigerated due to the fact that it does not contain a substantial amount of a matrix resin, in contrast to pre-impregnated materials.
    [0080] Unidirectional fibers in dry tape are high strength fibers adapted for structural reinforcement of high strength composites. To this end, unidirectional fibers can be made from high strength materials such as carbon, graphite, glass and aramid.
    [0081] The non-woven film is a lightweight material that may contain additional binding/hardening agents/particles. The presence of the non-woven film improves in-plane permeability of the tape and favors in-plane resin flow. Additionally, the film provides additional stability to the unidirectional fiber layer. An additional benefit of the film is that it can be used as a carrier for composite hardening particles, fibers, nanoparticles or other fillers such as intumescents, flame retardants in the interlaminar region.
    [0082] The binding materials described herein contribute to the low volume property of dry tape. When using polymeric non-woven films, the preferred softening point of polymeric films and binders is 160°C or less (as measured by Differential Scanning Calorimetry) in order to allow the tapes to bond together and form a preform consolidated at acceptable machine speeds. EXAMPLES
    [0083] Six different types of dry tapes were produced with or without the binders as indicated in Table 1. Each tape had a non-woven nylon film of copolyamide fibers (BR8 from Protechnic, France) bonded to one or both sides of a layer of unidirectional carbon fibers, wherein the film had an areal weight of 6 gsm and a melting point of about 155°C (measured by Differential Scanning Calorimetry using a temperature ramp test of 50°C to 350 °C with a ramp rate of 5°C/min rate). Binder 1 contained a combination of epoxy resins and PES-PEES copolymer and, if applied, was present on the top and bottom surfaces of the unidirectional fiber layer. Binder 2 contained a copolymer of polyhydroxyether and polyurethane and, if applied, was present throughout the tape. Binder 1 was applied as particulates and Binder 2 was applied as an emulsion. TABLE 1 - Dry tapes with thermoplastic films


    [0084] Another dry tape structure having a non-woven carbon film bonded to unidirectional fibers in place of nylon film was fabricated. Table 2 summarizes the structure of the tape. This tape had a non-woven film of carbon fibers bonded to one side of the unidirectional carbon fibers and contained both Binder 1 and 2. TABLE 2 - Dry tape with carbon film

    [0085] 24-layer preform stacks with the sequence of [+45/0/-45/90] were constructed using the dry strips shown in Table 1 and Table 2. The preform stacks were then constructed. vacuum bagged and exposed for 15 minutes at 130°C or 165°C and for 30 seconds at 165°C to see the effect of temperature on the volume of the preform. Temperatures were selected with respect to the melting point of the nylon film (i.e., 155°C). Exposing the tapes for 30 seconds at 165°C was more in line with typical ATL/AFP processing conditions. Once the heating cycle was complete, the preforms were vacuum cooled. Thickness measurements were made with a micrometer and were collected according to a sampling of locations (bottom web and cross web), each location was measured once. The results are summarized in Tables 3A and 3B. TABLE 3A

    TABLE 3B

    [0086] As mentioned above, the conditions of 165°C/30 s are representative of an automated fiber laying process (AFP), in which, in particular, the short exposure of the material to heat is due to the nature of the process. AFP, while heat is adjusted to adhere the deposited material. Note that the 15 minute warm-up period is not representative of an AFP process, but of a manual deposition pre-compaction process. The thickness of the preform constructed under these conditions can then be compared to the target cure layer thickness (cpt) of a desired composite. Equation 1 below can be used to derive the cpt of a composite as long as the composite fiber volume fraction, fiber density and areal fiber weight of each layer are known.
    where cpt = curing layer thickness (mm) Fd = fiber density (g/cm3) FVF = composite fiber volumetric fraction FAW = fiber areal weight (g/m2)
    [0087] Table 4 below provides the cpt of each material and the change in volume between the preform stage and the cured composite stage. The fiber density and fiber areal weight of each material are given in Table 4 and the cpt was derived according to Equation 1 assuming a fiber volume fraction of 57% which is a realistic target for this type of composite material and this type of composites manufacturing process, namely AFP and resin infusion. TABLE 4

    [0088] The last column of Table 4 provides the change in volume from the preform stage to the cured composite stage and it can be seen that the material based on Tape 2A has the highest level of degradation (12.5%) . Tape 2A did not contain Binder 1 or Binder 2. Comparison materials 3B and 4 had lower pre-compaction performance, as both were manufactured with tapes containing Binder 1 and 2. Pre-compaction material 3A it is approximately half of 2A material. This was achieved due to the addition of binder 1 to tape 2A.
    [0089] Although material 1A has achieved a low pre-compaction performance from the preform to the composite, this material is not actually viable since it is not stable and cannot be used in an automated process or even in a manual approach. However, it highlights the effect on preform volume due to the use of a single thermoplastic film versus two thermoplastic films. The material with two thermoplastic films is processable in an AFP machine but produces a larger volume than materials containing Binders 1 and 2.
    [0090] As such, the benefits of having Binders 1 and 2 have been clearly demonstrated in these examples. As a general rule, a pre-compression (ie reduction in volume) of up to 10% of the maximum is accepted to minimize materials encountered with pre-compression, such as tool setting, preform damage and so on. And as the thickness of the preform grows to a size of 10mm or even 20mm - in the example above it was a laminate of around 5mm - the impact on volume becomes even more important and it can be expected that the Thickness difference between preform and cured composite part to increase, which makes the use of Binders 1 and 2 even more desirable to control preform volume. For thick composite parts, material 2A would be an unacceptable proposition, while materials 3B and 4, which contain both Binder 1 and 2 to maintain a low volume preform, would be favored.
    权利要求:
    Claims (15)
    [0001]
    1. Preform, characterized in that it is configured to receive liquid resin in a liquid molding process, said preform having an initial thickness T1 and comprising a plurality of superimposed fibrous tapes deposited by an automated placing process, on that each tape comprises a layer of unidirectional fibers which are aligned parallel to each other, a non-woven film bonded to at least one side of the unidirectional fiber layer and two different binding materials distributed on at least one side of the unidirectional fiber layer and penetrated through portions of the non-woven film, or distributed throughout the tape, including in the spaces between the unidirectional fibers and in portions of the film, the first binding material is: i. a binder which is a solid at a temperature of up to 50°C, having a softening point at a temperature in the range of 75°C to 125°C as measured by Differential Scanning Calorimetry (DSC) and comprising a combination of epoxy resin and thermoplastic polymer, but is devoid of any catalyst or crosslinking agent that is active above 75°C; or ii. a composition comprising: at least one multifunctional epoxy resin; at least one thermoplastic polymer; and at least one surfactant selected from anionic surfactants and nonionic surfactants; and the second binding material is iii. partially or fully crosslinked copolymer of polyhydroxyether and polyurethane; the tape, including the non-woven film, is porous and permeable to a liquid resin to be used in a subsequent liquid molding process; and the preform exhibits a low volume property on heating, as determined by the heating and forming process of the automated placement process.
    [0002]
    2. Preform according to claim 1, characterized in that the surfactant in the binding material (ii) is selected from: a) non-ionic surfactant which is a mono- or multifunctional block or graft block copolymers comprising hydrophilic and hydrophobic blocks; b) anionic surfactant which is represented by the following formula: A—R where R is an alkyl, aryl, aryl-alkyl, or alkylene chain having 4-50 carbon atoms (C4 to C50); and A is lithium, sodium, potassium, ammonium, quaternary ammonium amine salt of a carboxylic, sulfonic or phosphoric acid group; and c) a combination of nonionic surfactant and anionic surfactant.
    [0003]
    3. Preform according to claim 1 or 2, characterized in that the first binding material is material (i).
    [0004]
    4. Preform according to any one of the preceding claims, characterized in that the first binding material is material (ii).
    [0005]
    5. Preform according to any one of the preceding claims, characterized in that the non-woven film of the tape is in the form of randomly oriented fibers; fibers oriented in a pattern (including a grid pattern); or a porous membrane.
    [0006]
    6. Preform according to any one of the preceding claims, characterized in that each tape comprises two non-woven thermoplastic fiber films bonded to opposite sides of the unidirectional fiber layer.
    [0007]
    7. Preform according to any one of the preceding claims, characterized in that each tape comprises a non-woven film of carbon fibers bonded to one side of the unidirectional fiber layer.
    [0008]
    8. Preform according to any one of the preceding claims, characterized by the fact that each tape has a width of 0.1 cm to 61 cm, a length that is at least 10 times its width and a thickness of 75 μ ma 300 μm or 100 μm to 250 μm.
    [0009]
    9. Preform according to any one of the preceding claims, characterized by the fact that the binding material(s) is (are) present in sufficient quantities to keep the fibers and the non-woven film together, but the total amount of binding material(s) is(are) less than 15% based on the total weight of the tape.
    [0010]
    10. Preform according to claim 1, characterized in that the first binding material is (ii) a composition comprising: at least one multifunctional epoxy resin; at least one thermoplastic polymer; and at least one surfactant selected from anionic surfactants and nonionic surfactants, and wherein the thermoplastic polymer in the binder material (ii) is a polyarylsulfone polymer comprising —(PhSO2Ph)— repeating units, wherein the —(PhSO2Ph) unit )— is present in the polyarylsulfone in such a proportion that, on average, at least two of said -(PhSO2Ph)- units are in sequence in each polymer chain present, where Ph is phenylene.
    [0011]
    11. A method for manufacturing a composite structure, characterized in that it comprises: a) depositing a plurality of dry fibrous strands by an automated laying process to form a multilayer preform having an initial thickness T1, each strand comprising : a layer of unidirectional fibers that are aligned parallel to each other, at least one non-woven film bonded to one side of the unidirectional fiber layer and two different binding materials distributed on at least one side of the unidirectional fiber layer and penetrated through portions of the non-woven film, or distributed throughout the tape including spaces between the unidirectional fibers and in portions of the non-woven film; b) infusing the preform with a liquid resin in a liquid molding process; and c) curing the resin-infused preform to form a composite structure, wherein the preform exhibits a low volume property on heating, as determined by the heating and forming process of the automated placement process, and the cured thickness of the composite structure, T2, is reduced from 0% to 10% of the initial preform thickness T1 (or 0.90 Ti < T2 < 1.00 Ti) and no further consolidation is required after the tape deposition step (a ), and where the first binding material is: i. a binder that is a solid at a temperature of up to 50°C, a softening point having a temperature in the range of 75°C to 125°C measured by DSC and comprising a combination of epoxy resin and thermoplastic polymer, but is empty any catalyst or crosslinking agent that is active above 75°C; or ii. a composition comprising at least one multifunctional epoxy resin; at least one thermoplastic polymer; and at least one surfactant selected from anionic surfactants and non-ionic surfactants; and the second binding material is iii. partially or fully crosslinked copolymer of polyhydroxyether and polyurethane.
    [0012]
    12. Method according to claim 11, characterized in that the thermoplastic polymer in the binding material (i) or (ii) is a polyarylsulfone polymer.
    [0013]
    13. Method according to claim 11 or 12, characterized in that the surfactant in the binding material (ii) is selected from: a) non-ionic surfactant which is a mono- or multifunctional block or graft block copolymers comprising hydrophilic and hydrophobic blocks; b) anionic surfactant which is represented by the following formula: A—R where R is an alkyl, aryl, aryl-alkyl, or alkylene chain having 4-50 carbon atoms (C4 to C50); and A is lithium, sodium, potassium, ammonium, quaternary ammonium amine salt of a carboxylic, sulfonic or phosphoric acid group; and c) a combination of nonionic surfactant and anionic surfactant.
    [0014]
    14. Method according to any one of claims 11 to 13, characterized in that each tape comprises a non-woven film bonded to one side of the unidirectional fiber layer, wherein said non-woven film is in the form of randomly arranged fibers , fibers oriented in a pattern, or porous membrane.
    [0015]
    15. Method according to any one of claims 11 to 14, characterized in that each tape comprises two non-woven films of thermoplastic fibers bonded to opposite sides of the unidirectional fiber layer or at least one non-woven film of bonded carbon fibers to one side of the unidirectional fiber layer.
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    同族专利:
    公开号 | 公开日
    RU2017102666A|2018-08-06|
    US20150375461A1|2015-12-31|
    WO2016003763A2|2016-01-07|
    ES2712869T3|2019-05-16|
    MX363040B|2019-03-06|
    CA2953778A1|2016-01-07|
    US10583615B2|2020-03-10|
    JP6654632B2|2020-02-26|
    KR102267769B1|2021-06-21|
    MX2016016711A|2017-11-02|
    EP3160720A2|2017-05-03|
    BR112016030776A2|2017-08-22|
    WO2016003763A3|2016-03-31|
    CN106470825A|2017-03-01|
    TW201614123A|2016-04-16|
    AU2015284500A1|2017-01-05|
    EP3160720B1|2018-11-21|
    RU2017102666A3|2019-01-30|
    KR20170026526A|2017-03-08|
    BR112016030776A8|2021-05-04|
    AU2015284500B2|2019-03-07|
    JP2017521291A|2017-08-03|
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    法律状态:
    2020-03-24| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-06-08| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-06-29| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 25/06/2015, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201462018857P| true| 2014-06-30|2014-06-30|
    US62/018,857|2014-06-30|
    PCT/US2015/037674|WO2016003763A2|2014-06-30|2015-06-25|Dry fibrous tape for manufacturing preform|
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