US20120141728A1 - Resin-soluble veils for composite article fabrication and methods of manufacturing the same - Google Patents

Resin-soluble veils for composite article fabrication and methods of manufacturing the same Download PDF

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Publication number
US20120141728A1
US20120141728A1 US13/307,383 US201113307383A US2012141728A1 US 20120141728 A1 US20120141728 A1 US 20120141728A1 US 201113307383 A US201113307383 A US 201113307383A US 2012141728 A1 US2012141728 A1 US 2012141728A1
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United States
Prior art keywords
veil
fibers
temperature
less
polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
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US13/307,383
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English (en)
Inventor
Dominique Ponsolle
Robert Blackburn
Billy Harmon
Richard Price
Marc Doyle
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Cytec Technology Corp
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Cytec Technology Corp
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Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=45319385&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=US20120141728(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Cytec Technology Corp filed Critical Cytec Technology Corp
Priority to US13/307,383 priority Critical patent/US20120141728A1/en
Assigned to CYTEC TECHNOLOGY CORP. reassignment CYTEC TECHNOLOGY CORP. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: BLACKBURN, ROBERT, PRICE, RICHARD, DOYLE, MARC, HARMON, BILLY, PONSOLLE, DOMINIQUE
Publication of US20120141728A1 publication Critical patent/US20120141728A1/en
Priority to US14/566,072 priority patent/US9902118B2/en
Abandoned legal-status Critical Current

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    • DTEXTILES; PAPER
    • D04BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04HMAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4382Stretched reticular film fibres; Composite fibres; Mixed fibres; Ultrafine fibres; Fibres for artificial leather
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K26/00Working by laser beam, e.g. welding, cutting or boring
    • B23K26/36Removing material
    • B23K26/38Removing material by boring or cutting
    • B23K26/382Removing material by boring or cutting by boring
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29BPREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
    • B29B11/00Making preforms
    • B29B11/14Making preforms characterised by structure or composition
    • B29B11/16Making preforms characterised by structure or composition comprising fillers or reinforcement
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C43/00Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor
    • B29C43/22Compression moulding, i.e. applying external pressure to flow the moulding material; Apparatus therefor of articles of indefinite length
    • B29C43/24Calendering
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
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    • B29C48/03Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
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    • B29C48/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25Component parts, details or accessories; Auxiliary operations
    • B29C48/36Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die
    • B29C48/365Means for plasticising or homogenising the moulding material or forcing it through the nozzle or die using pumps, e.g. piston pumps
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    • B29CSHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
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    • B29C70/40Shaping or impregnating by compression not applied
    • B29C70/42Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
    • B29C70/44Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using isostatic pressure, e.g. pressure difference-moulding, vacuum bag-moulding, autoclave-moulding or expanding rubber-moulding
    • B29C70/443Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using isostatic pressure, e.g. pressure difference-moulding, vacuum bag-moulding, autoclave-moulding or expanding rubber-moulding and impregnating by vacuum or injection
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
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    • B29C70/40Shaping or impregnating by compression not applied
    • B29C70/42Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles
    • B29C70/46Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs
    • B29C70/48Shaping or impregnating by compression not applied for producing articles of definite length, i.e. discrete articles using matched moulds, e.g. for deforming sheet moulding compounds [SMC] or prepregs and impregnating the reinforcements in the closed mould, e.g. resin transfer moulding [RTM], e.g. by vacuum
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    • B32B5/02Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
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    • B32B5/00Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B32LAYERED PRODUCTS
    • B32BLAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04Interconnection of layers
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04Reinforcing macromolecular compounds with loose or coherent fibrous material
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/24Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
    • C08J5/246Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs using polymer based synthetic fibres
    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01DMECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00Formation of filaments, threads, or the like
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    • D04H1/00Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y10T442/609Cross-sectional configuration of strand or fiber material is specified

Definitions

  • Liquid resin infusion is a process used to manufacture fiber-reinforced composite articles and components for use in a range of different industries including the aerospace, transport, electronics, building and leisure industries.
  • the general concept in LRI technology involves infusing resin into a fiber reinforcement, fabric or a pre-shaped fibrous reinforcement (“preform”) by placing the material or preform into a mold (two-component mold or single-sided mold) and then injecting resin under high pressure (or ambient pressure) into the mold cavity or vacuum bag sealed single-sided mold.
  • the resin infuses into the material or preform resulting in a fiber-reinforced composite article.
  • LRI technology is especially useful in manufacturing complex-shaped structures which are otherwise difficult to manufacture using conventional technologies.
  • Variation of liquid resin infusion processes include, but are not limited to, Resin Infusion with Flexible Tooling (RIFT), Constant Pressure Infusion (CPI), Bulk Resin Infusion (BRI), Controlled Atmospheric Pressure Resin Infusion (CAPRI), Resin Transfer Molding (RTM), Seemann Composites Resin Infusion Molding Process (SCRIMP), Vacuum-assisted Resin Infusion (VARI) and Vacuum-assisted Resin Transfer Molding (VARTM).
  • RIFT Resin Infusion with Flexible Tooling
  • CPI Constant Pressure Infusion
  • BRI Bulk Resin Infusion
  • CAPRI Controlled Atmospheric Pressure Resin Infusion
  • RTM Resin Transfer Molding
  • SCRIMP Seemann Composites Resin Infusion Molding Process
  • VARI Vacuum-assisted Resin Infusion
  • VARTM Vacuum-assisted Resin Transfer Molding
  • One method to increase the toughness in composite articles manufactured by liquid resin infusion processes involves the use of non-woven veils of resin-soluble thermoplastic interposed between plies of dry structural reinforcement fiber.
  • the veil may be comprised of a random mat of continuous or chopped polymer fibers.
  • the fibers may be yarns or monofilaments of spun strands.
  • Prior art resin-soluble thermoplastic veils are known to suffer from various shortcomings including bulkiness, low strength, uneven fabric areal weight (FAW) and premature dissolution. Variable uniformity of the FAW and certain characteristics of the fibers comprising the veil, e.g., fineness, directly affect the rate of dissolution of the fibers as well as the distribution evenness of the toughening agent in the composite. Bulkiness affects composite manufacture as well as composite cure ply thickness (CPT).
  • CPT composite cure ply thickness
  • a non-woven engineered veil comprised of a plurality of fibers having a diameter of between 10 microns and 16 microns wherein less than 20% of the fibers have a diameter of less than 8 microns, the veil having a fabric areal weight variation of less than 10% across the width of the textile, the veil having a thickness achieved by a calendering process is herein disclosed.
  • the veil may have a fabric areal weight of between 5 grams per square meter and 80 grams per square meter and a thickness of between 20 ⁇ m and 90 ⁇ m.
  • a material comprising the plurality of fibers may be a polymer having a native solid phase and adapted to undergo at least partial phase transition to a fluid phase on contact with a component of a curable composition in which the polymer is soluble at a temperature which is less than the temperature for substantial onset of curing of the curable composition and which temperature is less than the inherent melting temperature of the non-woven engineered textile.
  • the polymer may have a melt flow index of between 18 and 38.
  • the non-woven engineered veil further comprises a plurality of perforations throughout the veil.
  • the veil may be manufactured by a melt-extrusion process such as melt blown or spunbond.
  • a melt-extrusion process such as melt blown or spunbond.
  • at least one processing parameter of the process may be set to be within a predetermined range, above a predetermined threshold or below a predetermined threshold, wherein at least one processing parameter includes one of melt pump speed, collector rate speed, airflow rate, and airflow temperature.
  • a method of manufacturing a non-woven engineered veil using a melt-blown process comprising: (a) increasing a melt pump speed while simultaneously decreasing an airflow rate; (b) loading a material into an extruder wherein the material is a polymer having a native solid phase and adapted to undergo at least partial phase transition to a fluid phase on contact with a component of a curable composition in which the polymer is soluble at a temperature which is less than the temperature for substantial onset of curing of the curable composition and which temperature is less than the inherent melting temperature of a resultant non-woven engineered veil; and (c) causing the polymer to be extruded from a die head in the farm of fibers and onto a moving collector, the fibers forming a non-woven engineered veil wherein increasing the melt pump speed while decreasing the airflow rate provides fibers having a diameter of between 10 microns and 16 microns wherein less than 20% of the fibers have a diameter of less than 8 microns, the veil having a fabric are
  • the method may further comprise (d) subjecting the non-woven engineered veil to a calendering process.
  • the veil may have a fabric areal weight of between 5 grams per square meter and 80 grams per square meter and a thickness of between 20 ⁇ m and 90 ⁇ m.
  • the method further comprises (e) subjecting the veil to an off-line perforation process, the off-line perforation process effectuated by one of a needle or a laser.
  • a preform for composite article manufacturing comprising: (a) at least one structural component comprising reinforcement fibers; (b) at least one non-woven engineered veil contacting the structural component, the veil comprised of a plurality of fibers having a diameter of between 10 microns and 16 microns wherein less than 20% of the fibers have a diameter of less than 8 microns, the veil having a fabric areal weight variation of less than 10% across the width of the veil, the plurality of fibers comprised of polymer having a native solid phase and adapted to undergo at least partial phase transition to a fluid phase on contact with a component of a curable composition in which the polymer is soluble at a temperature which is less than the temperature for substantial onset of curing of the curable composition and which temperature is less than the inherent melting temperature of the non-woven engineered textile is herein disclosed.
  • the polymer may have a melt flow index of between 18 and 38.
  • the structural component may be in the form of a plurality of adjacent reinforcement fiber layers and the non-woven engineered veil may be in the form of a plurality of resin-soluble thermoplastic veils interposed between pairs of adjacent reinforcement fiber layers.
  • the preform may be adapted for resin infusion.
  • the veil may have a fabric areal weight of between 5 grams per square meter and 80 grams per square meter and a thickness of between 20 ⁇ m and 90 ⁇ m as a result of a calendering process.
  • the preform further comprises a plurality of perforations throughout the veil.
  • a method of manufacturing a composite article using a liquid resin infusion process comprising: (a) arranging a plurality of structural components comprising reinforcement fibers within a mold; (b) interleafing a plurality of non-woven engineered veils with the plurality of structural components, the plurality of veils comprised of a plurality of fibers having a mean diameter of between 10 microns and 16 microns Wherein less than 20% of the fibers have a diameter of less than 8 microns, and a fabric areal weight variation of less than 10% across the width of the textile, the interleafed arrangement forming a preform; (c) contacting the preform with a resin wherein the resin is at an initial temperature of less than 75 ° C.; (d) heating the preform to a predetermined temperature threshold wherein a majority of the fibers are dissolved before the predetermined temperature threshold is reached; and (e) allowing the preform to cure while the preform is held at the predetermined temperature threshold for a predetermined time period is herein
  • the predetermined temperature threshold may be about 180 ° C.
  • the plurality of fibers may comprise a polymer having a native solid phase and adapted to undergo at least partial phase transition to a fluid phase on contact with a component of a curable composition in which the polymer is soluble at a temperature which is less than the temperature for substantial onset of curing of the curable composition and which temperature is less than the inherent melting temperature of the non-woven engineered veil.
  • the polymer may have a melt flow index of between 18 and 38.
  • the textile may have a fabric areal weight of between 5 grams per square meter and 80 grams per square meter and a thickness of between 20 ⁇ m and 90 ⁇ m.
  • FIG. 1 is a schematic of a meltblowing manufacturing process according to an embodiment of the invention.
  • FIG. 2 is a chart comparing veil fiber diameter before and after optimization of the manufacturing process according to embodiments of the invention.
  • FIG. 3 is a chart comparing veil cross-web FAW profiles across 20 gsm and 40 gsm veils before and after the optimization of the manufacturing process according to embodiments of the invention.
  • FIG. 4 is a schematic of a calendering process according to an embodiment of the invention.
  • FIG. 5 is a chart comparing a thickness profile across a 40 gsm veil before and after calendering.
  • FIG. 6 is a chart comparing an air porosity profile of a 40 gsm veil before and after calendering.
  • FIG. 7 are photographs comparing a composite laminate of non-calendered veil, a composite laminate of calendered veil according to embodiments of the invention, and a composite laminate with no veil.
  • FIG. 8 is graph comparing a resin injection cycle of a thermoplastic resin-soluble yarn and a thermoplastic resin-soluble according to embodiments of the invention.
  • FIG. 9 are photographs of the dissolution of fibers of a veil according to embodiments of the invention.
  • FIG. 10 illustrates a lay-up of structural components and resin-soluble thermoplastic veils according to an embodiment of the invention.
  • Embodiments of the invention are directed to non-woven engineered veils, which include non-woven, resin-soluble thermoplastic veils for use in liquid resin infusion processes, methods of manufacturing non-woven engineered veils for use in liquid resin infusion processes, and methods of manufacturing composite articles using non-woven engineered veils for use in liquid resin infusion applications.
  • the non-woven engineered veils according to embodiments of the invention have improved characteristics including, but not limited to, increased uniformity and decreased thickness relative to prior art veils. These characteristics translate into improvements in the processing of a composite article including, but not limited to, a substantial or complete elimination in premature dissolution of the veil during cure.
  • the resultant composite article also realizes improvements including but not limited to, distribution evenness of the toughening agent throughout the composite and a reduced composite ply thickness.
  • the non-woven engineered veil includes a plurality of resin-soluble thermoplastic fibers having at least one of the following characteristics: (a) substantial uniformity as a result of (i) fibers having a mean diameter within a predetermined range with 20% of the fibers having a diameter of less than a predetermined threshold; and (ii) veil having a fiber areal weight variation within a predetermined range; (h) veil having a thickness within a predetermined range; and/or (c) veil having a permeability characteristic resulting from off-line perforation of the veil.
  • a method of manufacturing the non-woven engineered veil is performed by a melt-blown process wherein at least one processing condition and/or equipment condition including, but not limited to, melt pump speed, airflow rate, collector speed, airflow temperature, die head temperature, distance of conveyer to die head and die hole diameter is controlled and/or manipulated within predetermined parameters.
  • the method is further improved by subjecting the resultant non-woven engineered veil to a calendaring process resulting in controlled porosity and improved strength of the veil as well as a reduction in preform bulk factor which is essential in LRI applications.
  • the method is further improved by subjecting the calendered veil to off-line perforation resulting in increased permeability for increased resin diffusion in LRI applications.
  • a method of manufacturing composite articles using the non-woven engineered veil is performed by a resin infusion process wherein the dissolution of the veil is controlled as a result of one or more characteristics of the manufactured veil resulting in substantial or complete elimination of premature dissolution and substantial or complete even distribution of toughening throughout the composite.
  • a “veil” is an ultrathin, nonwoven mat comprised of organic fibers and combined with one or more plies to create composite articles. Veils may be used for toughening when interposed between plies of a fabric lay-up.
  • a “mat” is an nonwoven textile fabric made of fibrous reinforcing material, such as chopped filaments (to produce chopped strand mat) or swirled filaments (to produce continuous strand mat) with a binder applied to maintain form.
  • a “resin-soluble polymer” is a polymer in a solid phase within a predetermined temperature range and adapted to undergo at least partial phase transition to a fluid phase upon contact with a component of a curable composition in which the polymer is soluble at a temperature which is less than the temperature for substantial onset of gelling and/or curing of the curable composition and which temperature is less than the inherent melting temperature of the resin-soluble thermoplastic veil.
  • resin-soluble polymers include those identified in U.S. Pub. No. 2006/0252334 LoFaro et al. which is hereby incorporated by reference.
  • Methods of manufacturing the non-woven engineered veil according to embodiments of the invention include, but are not limited to, drylaying, airlaying, meltblowing, spunbonding, wetlaying and carding with or without cross-lapping.
  • the veil according to embodiments of the invention is manufactured through meltblowing.
  • a meltblowing manufacturing process begins with a solid phase polymer in powder or granular form.
  • the polymer may be melted at between about 200° C. and 400 ° C. and extruded through a plurality of spinnerets.
  • the orifice size of the spinneret may be between about 0.1 microns to about 1000 micron.
  • Air having a temperature in the range of about 250° C. to 500° C. may be blown throughout the fibers extruded onto a conveyor from the spinnerets to thin the fibers into super thin fibers and to randomize the fibers into a veil.
  • FIG. 1 is a schematic of a meltblowing manufacturing process according to an embodiment of the invention.
  • polymer material e.g., pellets or granules
  • the extruder 102 comprises a barrel and a screw (not shown) within the extruder 102 to rotate the polymer material along the walls of the barrel.
  • the barrel of the extruder 102 is heated.
  • the polymer material moves along the walls of the barrel, it melts due to the heat and friction of viscous flow and the mechanical action between the screw and the barrel.
  • Pressured molten polymer material is then fed into the gear pump 106 .
  • the gear pump 106 is a positive displacement and constant volume device for uniform melt delivery to the die assembly 108 .
  • the gear pump 106 ensures consistent flow of molten polymer material and provides metering of and pressure to the molten polymer material.
  • the gear pump 106 includes two inter-meshing and counter-rotating toothed gears 106 a, 106 b. Positive displacement results from the filling of each gear tooth with polymer material on the suction entrance of the pump (i.e., upstream following extruder 102 ) and carrying the polymer material around to the discharge exit of the pump (i.e., downstream towards a die assembly 108 ).
  • the die assembly 108 generally includes a feed distribution (e.g., T-type and coat hanger type), a die head and air manifolds.
  • the feed distribution balances both the flow and the residence time of the polymer material across the width of the die;
  • the die head is generally a wide, hollow and tapered piece of metal having several hundred orifices for extruding molten polymer material;
  • the air manifolds supply high velocity air to the molten polymer material as it is being extruded through the die head.
  • An air compressor 112 supplies the high velocity air which generally passes through a heater 114 before being fed into the die assembly 108 .
  • a moving collector screen 116 collects the cooling material.
  • a suction box/suction blower 118 located beneath the collector screen 116 sucks the high velocity air which increases the rate of web formation of the resulting extruded polymer fibers.
  • At least one processing condition and/or equipment condition including, but not limited to, melt pump speed., collector speed, airflow rate, airflow temperature, die head temperature, die hole diameter and distance of conveyer to die head may be controlled and/or manipulated within predetermined parameters to produce a non-woven engineered veil for use in resin transfer molding applications.
  • melt pump speed. collector speed
  • airflow rate airflow temperature
  • die head temperature die hole diameter and distance of conveyer to die head
  • “advantageous characteristics” include, but are not limited to, coarser fibers, low percentage of fine fibers (i.e., less than 20% of the fibers having a diameter of less than 8 ⁇ m), increased fiber uniformity (i.e., a narrower distribution of the measured fiber diameter), low FAW variation (i.e., the change in weight of the veil through a roll or a batch wherein the weight is measured at different locations of the veil including, but not limited to, cross-web and down-web), high veil tensile strength (i.e., the ability of the veil being able to meet certain requirements including, but not limited to, handling and manufacturing) and high veil quality.
  • uniform veil and high quality veil results in more uniform and higher quality preform, e.g., little or no tearing of the veil during preform manufacture, uniform ply thickness, etc., directly resulting in more uniform resin infusion, i.e., diffusion of the resin in the part and a smoother and more controlled resin front.
  • manipulation and control of certain parameters according to embodiments of the invention resulted in a fiber diameter range of between 10 microns and 16 microns as compared to conventional fiber diameters in a range of between 1 micron and 8 microns.
  • the melt pump speed was increased relative to conventional melt pump speeds.
  • a melt pump speed between about fourteen (14) rpm and about sixteen (16) rpm provided advantageous characteristics including, but not limited to, coarser fibers, low percentage of fine fibers (i.e., less than 20% of the fibers having a diameter of less than 8 ⁇ m), high FAW, high veil strength and high veil quality.
  • FAW variation (low) was also realized as an improvement, however, not to the same extent of those characteristics previously listed.
  • Applicants also discovered that either an increase or decrease in melt pump speed had a limited influence on increased fiber diameter uniformity.
  • the increased melt pump speed resulted in increased throughput of the molten polymer material through the die head and less stretch which correlates to coarser fibers.
  • the airflow rate was adjusted relative to conventional airflow rates. Applicants discovered that decreasing the airflow rate to between about forty (40) percent (%) and fifty (50) percent (%) provided advantageous characteristics including, but not limited to, coarser fibers and low percentage of fine fibers (i.e., less than 20% of the fibers having a diameter of less than 8 ⁇ m). FAW variation (low) and veil quality (high) were also realized as improvements, however, not to the same extent of those characteristics previously listed. Applicants also discovered that increasing the airflow rate to above fifty (50) percent (%) provided limited improvements including, but not limited to, increased fiber diameter uniformity (limited influence) and high veil strength. Applicants also discovered that either an increase or decrease in airflow rate had a limited or no influence on FAW.
  • collector rate speed was adjusted as a function of melt pump speed. Applicants observed that decreasing the collector rate speed to between about thirty-live (35) feet per minute (FPM) and forty (40) FPM relative to a melt pump speed between about 12 and 16 rpm provided advantageous characteristics including, but not limited to, coarser fibers, fiber diameter uniformity and a low FAW variation. Conversely, Applicants discovered that increasing the collector speed rate to between about seventy (70) FPM and eighty (80) FPM relative to a melt pump speed between about 12 and 16 rpm provided limited improvements including, but not limited to, low percentage of fine fibers (i.e., less than 20% of the fibers having a diameter of less than 8 ⁇ m) and high veil strength. In some embodiments, the collector speed and the melt pump speed may be adjusted in tandem to optimize throughput. It should be appreciated that characteristics were observed for veils targeted between about twenty (20) and forty (40) gsm FAW.
  • airflow temperature was adjusted relative to conventional airflow temperatures. Applicants also discovered that increasing the airflow temperature to about 680° F. provided advantageous characteristics including, but not limited to, increased fiber diameter uniformity and low FAW variation. High veil strength was also realized as an improvement, however, not to the same extent of those characteristics previously listed. Conversely, Applicants discovered that decreasing the airflow temperature to about 650° F. provided limited improvements including, but not limited to, coarser fibers and a low percentage of fine fibers (i.e., less than 20% of the fibers having a diameter of less than 8 ⁇ m).
  • an increased melt pump rate combined with a decreased airflow rate (and, in some embodiments, an increase in air temperature) for polymer-based veils having an MFI of between twenty (20) and twenty-eight (28) have the greatest effect on providing non-woven engineered veils having superior characteristics relative to conventional veils. More specifically, a melt pump rate of between 12 and 16 rpm, more narrowly between 14 and 16 rpm, and an airflow rate of between forty (40) % and fifty (50) % provide veils having superior characteristics relative to conventional veils.
  • these processing parameters provide non-woven engineered veils having coarser fibers having a mean average fiber diameter greater than ten (10) ⁇ m (compared to less than 8 ⁇ m of conventional fibers) with a low percentage of fine fibers (i.e., 20% less than 8 pm diameter fibers), more particularly, fibers having a mean diameter of between 10 microns and 16 microns wherein less than 20% of the fibers have a diameter of less than 8 microns (see FIG. 2 ). Additionally, the distribution of the coarser fibers was more uniform throughout effectively increasing the uniformity of the veil.
  • these processing parameters provide non-woven engineered veils having improved uniformity which is measured by the fabric areal weight (FAW) variation.
  • the FAW is measured by measuring the weight of the veil at various points along the width thereof (cross web) or the length thereof (down web). The more closely the values match at each point, the more uniform the veil.
  • the FAW of non-woven engineered veils subjected to at least these processing parameters realized a forty (40) % reduction in FAW variation relative to conventional veils. More particularly, the fabric areal weight variation of less than ten (10) % across the width of the veil (cross web) (see FIG. 3 ).
  • Veils manufactured according to embodiments of the invention had a FAW of between about five (5) grams per square meter (gsm) and eighty (80) grams per square meter, more narrowly between about fifteen (15) gsm and sixty (60) gsm, more narrowly, between about twenty (20) gsm and forty (40) gsm.
  • processing conditions optimized may be interdependent on equipment characteristics and other parameters including, but not limited to: die characteristics such as die hole diameter, number of die holes per inch, die head temperature (edge), die head temperature (center), die head screen mesh size, die head screen pressure; air gap; set back; extruder characteristics such as extruder speed and extruder temperature; melt pump temperature; collector characteristics such as collector vacuum; distance of die head to collector; coat hanger and die design.
  • die characteristics such as die hole diameter, number of die holes per inch, die head temperature (edge), die head temperature (center), die head screen mesh size, die head screen pressure; air gap; set back; extruder characteristics such as extruder speed and extruder temperature; melt pump temperature; collector characteristics such as collector vacuum; distance of die head to collector; coat hanger and die design.
  • the polymer is a polymer having a characteristic of being in a solid phase and adapted to undergo at least partial phase transition to a fluid phase on contact with a component of a curable composition in which the polymer is soluble at a temperature which is less than the temperature for substantial onset of gelling and/or curing of the curable composition and which temperature is less than the inherent melting temperature of the non-woven engineered veil.
  • the MFI of the polymer may also affect the dissolution rate.
  • the polymer has a melt flow index of between about eighteen (18) MFI and about thirty-eight (38) MFI, preferably about twenty (20) MFI and twenty-eight (28) MFI. That is, the polymer has a high viscosity ( i ) and, in some embodiments, a narrow molecular distribution throughout.
  • Non-woven engineered veils include polyaromatic thermoplastic polymers such as polyethersulphone and more preferably a combination of polyethersulphone-etherketone and of polyetherethersulphone.
  • Table 1 summarizes the processing parameters as pertains to their affects on the non-woven engineered veils manufactured according to embodiments of the invention:
  • FIG. 4 is a schematic of a calendering process according to an embodiment of the invention.
  • a roll of non-woven engineered veil is run through a calender 400 .
  • the calender 400 includes two adjacent rollers 402 , 404 in which the engineered textile is passed through.
  • Roller 402 may be made of steel while roller 404 may made of steel or a synthetic material.
  • Calender 400 may include at least one heated nip roll. The combination of applied pressure with temperature to the engineered veil after passing through calender 400 may result a thinner engineered veil relative to the pre-calendered engineered veil.
  • Veils may be interleafed with non-crimp fabrics or NCFs to form a preform in resin infusion processes.
  • Non-crimped fabrics are plies of unidirectional fibers consolidated together via a stitching process.
  • the resultant layers should be as thin as practicable, referred to as low “preform bulkiness.”
  • Low veil thickness is critical as such thickness is a direct function of preform bulkiness.
  • preform dimensions should not exceed between five (5) % and ten (10) % of the mold dimensions.
  • Conventional veils add up to twenty (20) % more to preform bulkiness.
  • the non-woven engineered veil can he subjected to a calendering step prior to composite article manufacturing using a resin transfer molding process.
  • the non-woven engineered veil is subjected to a calender having two steel rollers. Applicants discovered that the two steel rollers (in addition to other characteristics specific to the veil) resulted in a veil with a forty (40) to fifty (50) % decrease in thickness relative to veils experimentally calendered using a conventional calender apparatus having a steel roller and a synthetic roller.
  • Calendering process parameters also had an effect on the resultant calendered veils as discovered by Applicants.
  • Such calendering process parameters include, but are not limited to: calender pressure; calender temperature; calender speed, etc.
  • calender pressure For example, Applicants discovered that an increase in pressure to between 500 psi and 860 psi, preferably between 700 psi and 750 psi, relative to lower pressures (i.e., about 300 psi) had a positive effect on the resultant calendered veil.
  • Other calendering process parameters having a positive effect on the resultant calendered veil included a temperature of between 200° F. and 400° F., more narrowly between 200° F. and 300° F. (depending on the calendering speed) and a calendering speed of between five (5) and thirty (30) feet per minute.
  • the veils subjected to the calendering process as previously described were manufactured according to embodiments of the invention, i.e., non-woven engineered veils having fibers in a range of between ten (10) ⁇ m and fourteen (16) ⁇ m with a low percentage of fine fibers (i.e., 20% or less of fibers having an 8 pm diameter), high tensile strength and substantial FAW uniformity (i.e., a fabric areal weight variation of less than 10% across the width of the textile).
  • These veils had an average FAW of between twenty (20) gsm and forty (40) gsm and were reduced in thickness from between 250 ⁇ m and 500 ⁇ m (non-calendered) to between twenty (20) ⁇ m and ninety (90) ⁇ m (calendered) by subjecting the veil to the calendering step as previously described (see FIG. 4 ).
  • air permeability was measured at about 175 cfm.
  • air permeability was measured at about 500 cfm (see FIG. 6 ).
  • the minimum air permeability should be greater than 25 cfm and preferably greater than 50 cfm.
  • the calendered veil according to embodiments of the invention resulted in reduced bulk of the veil which translates into a reduced preform bulk factor. This is particularly important in close mold applications such as RTM where preform must fit appropriately in the mold in order for the mold to close (discussed previously).
  • this reduced preform bulk translates into a composite ply thickness (for a composite that includes a veil per ply layer) equivalent to the composite ply (thickness (CPT) of a composite made without a veil (see FIG. 7 ).
  • the picture on the left displays a composite laminate cross-section made of non-calendered veil layers; the picture on the center displays a composite laminate made of calendered veil according to embodiments of the invention; the picture on the right is a composite laminate made without any veil. Comparison of the laminates reveals that there are much reduced interface layers in the case of the calendered veil than for the non-calendered veil. This reduced bulkiness results in composites with higher fiber volume fraction.
  • ⁇ improvements of the calendered veil according to embodiments of the invention include, but are not limited to: an increase in veil tensile resistance which facilitates handling during preform construction; a smoother veil surface which reduces friction and allows for better lay-up of the carbon tows during NCF construction (discussed in more detail below); and/or a negligible effect on the optimized fiber diameter; and a negligible effect on drapeability.
  • the minimum value of tensile resistance in a 20 gsm non-calendered veil is about 0.1 pound per inch while the minimum value of tensile resistance in a 20 gsm calendered veil according to embodiments of the invention is about 0.3 pounds per inch, or an increase by a factor of three (3).
  • the non-woven engineered veils according to embodiments of the invention may be subjected to an off-line perforation technique prior to the manufacture of a composite article (e.g., through incorporation of a non-crimped fabric (NCF) or univeil product) to increase permeability and allow the resin to better diffuse throughout the preform during the resin injection process which in turn increases the through thickness resin diffusion.
  • NCF non-crimped fabric
  • This is specifically important in the case of the super thin veils which have a low permeability and would not be suitable for certain LRI applications (e.g., VaRTM) as the resin does not flow through the preform medium.
  • the perforation can be done at the time of the NCF manufacture when the veil is added to the carbon layers of the NCF.
  • the perforation of the veil can be done in a separate operation with very tiny needles that puncture the veil to create tiny holes.
  • the perforation may have a hole diameter of between 0.1 mm and 2.0 mm, and a hole density of between 1 and 100 per cm 2 depending on the desired permeability.
  • off-line perforation techniques include, but are not limited to, needle punching, roller pinning and laser perforation.
  • a laser beam is used to vaporize or burn off the material to create tiny holes. Hole geometry and density can easily be manipulated with this laser technique.
  • Non-woven engineered veils fabricated as previously described may be used in the manufacture of a curable composition resulting in a composite article.
  • such manufacturing comprises contacting a veil with a curable resin matrix for example by interleaving, impregnating, injecting or infusing, mixing and the like.
  • the veil is contacted with a resin (i.e., an epoxy) by injection such as used in LRI applications. Fibers comprising the veil typically dissolve throughout during a cure cycle.
  • Premature dissolution during a ramp-up phase of a cure cycle is a known limitation of conventional veils.
  • dissolution refers to the dissolving of fibers in the non-woven engineered veil during the cure cycle, i.e., after the veil is contacted with resin and heat is applied thereto. Premature dissolution occurs when dissolution occurs below the resin injection temperature.
  • the cure cycle typically includes a temperature ramp-up time period followed by a temperature dwell time period followed by a temperature ramp-down time period after injection of the resin (see FIG. 8 ). A substantial amount of dissolution of the yarn fibers is known to take place during the dwell time period. Dissolved yarn fibers become the toughening agent in the resultant composite article.
  • FIG. 9 show optical microscope photographs of the dissolution of the veil fibers during cure cycle temperature ramp up according to embodiments of the invention.
  • the resin temperature has been initiated and the veil is undissolved.
  • the veil fibers dissolve slowly. All fibers are fully dissolves at 110° C.
  • the shorter resin injection cure increased production (i.e., reduced manufacturing time) resulting to lower manufacturing costs.
  • Applicants also ascertained that dissolution of the fibers occurred at a suitable margin above the injection temperature (e.g., between 60-75° C.) as compared to conventional veils. Premature dissolution can compromise the integrity of the resulting composite article and, therefore, a substantial or complete elimination in premature dissolution of the veil during cure is highly beneficial.
  • a suitable margin above the injection temperature e.g., between 60-75° C.
  • FIG. 10 illustrates a lay-up of structural components and non-woven engineered veils according to an embodiment of the invention.
  • a “structural component” is an engineered fabric made of reinforcing fibers such as organic and inorganic polymers, carbon, glass, AramidTM.
  • suitable fabric types or configurations include, but are not limited to: woven fabrics such as polar weaves, plain woven fabrics, spiral weaves and uniweaves; multi-axial fabrics such as multi-warp knitted fabrics, non-crimp fabrics (NCF) and multi-directional fabrics; knitted fabrics braided fabrics; tailored fiber placement fabrics such as fiber placement and embroidered fabrics; non-woven fabrics such as mat-fabric, felts, veils and chopped strands mats and fabrics that are comprised of combinations thereof.
  • a plurality of carbon fabrics can be interleafed with a plurality of resin-soluble thermoplastic veils according to an embodiment of the invention in an RTM tool to create a preform.
  • a resultant composite article results when subjected to a liquid resin infusion process as previously described.
  • Non-woven engineered veils manufactured according to embodiments of the invention as previously described resulted in numerous advantages relative to conventional veils.
  • controlled veil fiber diameter and distribution, achieved through process optimization provided at least the following benefits: a shorter resin injection cure cycle of thermoplastic veils manufactured according to embodiments of the invention relative to yarn-based thermoplastic material; a controlled dissolution process (i.e., premature dissolution is eliminated through a careful fiber diameter selection in a range of 10 to 16 microns and resin injection temperature of 60 to 75° C.); a greater FAW uniformity of the veil translating into improved composite article characteristics and performance through a more uniform dissolution of the fibers and therefore diffusion of the toughening agent.
  • reduced veil thickness achieved through a calendering step, provides at least the following benefits: veils with a thickness ranging between 20 to 90 ⁇ m, compared to non-calendered veils with a thickness ranging between 250 and 500 ⁇ m; veils that retain nonwoven characteristics such as being porous and flexible (i.e. not like a film); reduced preform bulk factor (particularly important in close mold applications such as RTM); and CPT equivalent to a composite made without a veil.
  • controlled fiber areal weights both down web and cross web, achieved through process optimization, provided at least the following benefits: greater uniformity of the non-woven veil (e.g. strength, thickness, air permeability), translating in improved veil characteristics and performance; a more uniform distribution of the toughening fibers throughout the resultant composite article and improved composite performance.

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  • Nonwoven Fabrics (AREA)
  • Reinforced Plastic Materials (AREA)
  • Laminated Bodies (AREA)
  • Moulding By Coating Moulds (AREA)
US13/307,383 2010-12-01 2011-11-30 Resin-soluble veils for composite article fabrication and methods of manufacturing the same Abandoned US20120141728A1 (en)

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CN (1) CN103221459B (de)
AU (1) AU2011336966B2 (de)
BR (1) BR112013012884B1 (de)
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US20130192434A1 (en) * 2010-12-24 2013-08-01 Toray Industries, Inc Method for producing carbon fiber aggregate, and method for producing carbon fiber-reinforced plastic
US20160089853A1 (en) * 2014-09-30 2016-03-31 The Boeing Company Filament Network for a Composite Structure
WO2017200560A1 (en) * 2016-05-19 2017-11-23 Cerex Advanced Fabrics, Inc. Items made with corrosion resistant nonwoven fabrics
US20190061290A1 (en) * 2015-08-05 2019-02-28 Hexcel Composites Limited Moulding materials with improved surface finish
US10792837B2 (en) 2015-05-22 2020-10-06 Borealis Ag Process for manufacturing of a fibre-reinforced polymer composition
US20220227099A1 (en) * 2019-05-09 2022-07-21 Teijin Carbon Europe Gmbh Multiaxial textile fabric with discontinuous intermediate layer
US11628632B2 (en) * 2019-03-25 2023-04-18 The Boeing Company Pre-consolidated charges of chopped fiber for composite part fabrication

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CN104552934A (zh) * 2013-10-22 2015-04-29 谢贤晓 织物成形方法
AU2016222310B2 (en) * 2016-08-29 2022-09-29 The Boeing Company Method of locally influencing resin permeability of a dry preform
DE102016119866A1 (de) * 2016-10-18 2018-04-19 Reifenhäuser GmbH & Co. KG Maschinenfabrik Verfahren und Anlage zur Erzeugung eines Vlieses aus Fasern
CN108823810A (zh) * 2018-06-11 2018-11-16 浙江金三发非织造布有限公司 一种纺粘水刺工艺结合的非织造布成型技术
CN115467106B (zh) * 2022-08-25 2023-08-29 东华大学 一种用于制备多孔纱线的多功能溶液浸渍发泡一体化装置

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US20060240242A1 (en) * 2004-03-26 2006-10-26 Azdel, Inc. Fiber reinforced thermoplastic sheets with surface coverings
US7252729B2 (en) * 2004-12-29 2007-08-07 Owens-Corning Fiberglas Technology Inc. Polymer/WUCS mat for use in sheet molding compounds

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JP4511260B2 (ja) * 2004-06-22 2010-07-28 旭化成せんい株式会社 細幅テープおよび細幅テープ状物
CN101954245A (zh) * 2004-12-21 2011-01-26 旭化成纤维株式会社 分离膜支撑体的制造方法
WO2006121961A1 (en) * 2005-05-09 2006-11-16 Cytec Technology Corp. Resin-soluble thermoplastic veil for composite materials
JP5584224B2 (ja) 2008-10-23 2014-09-03 ヘクセル ランフォルセマン 複合部品の作製に適した新規な補強材料
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US20050064166A1 (en) * 2003-09-24 2005-03-24 Burrows Robert D. Fibrous veil for class a sheet molding compound applications
US20060240242A1 (en) * 2004-03-26 2006-10-26 Azdel, Inc. Fiber reinforced thermoplastic sheets with surface coverings
US7252729B2 (en) * 2004-12-29 2007-08-07 Owens-Corning Fiberglas Technology Inc. Polymer/WUCS mat for use in sheet molding compounds

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130192434A1 (en) * 2010-12-24 2013-08-01 Toray Industries, Inc Method for producing carbon fiber aggregate, and method for producing carbon fiber-reinforced plastic
US20160089853A1 (en) * 2014-09-30 2016-03-31 The Boeing Company Filament Network for a Composite Structure
US10632718B2 (en) * 2014-09-30 2020-04-28 The Boeing Company Filament network for a composite structure
US10792837B2 (en) 2015-05-22 2020-10-06 Borealis Ag Process for manufacturing of a fibre-reinforced polymer composition
US20190061290A1 (en) * 2015-08-05 2019-02-28 Hexcel Composites Limited Moulding materials with improved surface finish
WO2017200560A1 (en) * 2016-05-19 2017-11-23 Cerex Advanced Fabrics, Inc. Items made with corrosion resistant nonwoven fabrics
US11628632B2 (en) * 2019-03-25 2023-04-18 The Boeing Company Pre-consolidated charges of chopped fiber for composite part fabrication
US20220227099A1 (en) * 2019-05-09 2022-07-21 Teijin Carbon Europe Gmbh Multiaxial textile fabric with discontinuous intermediate layer

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BR112013012884B1 (pt) 2021-03-02
TW201228810A (en) 2012-07-16
BR112013012884A2 (pt) 2019-01-08
KR20130131389A (ko) 2013-12-03
CA2817369C (en) 2018-01-16
JP2014503700A (ja) 2014-02-13
EP2646500A1 (de) 2013-10-09
CN103221459B (zh) 2016-03-09
MY173821A (en) 2020-02-24
JP5897593B2 (ja) 2016-03-30
AU2011336966B2 (en) 2013-11-21
WO2012074778A1 (en) 2012-06-07
KR101784543B1 (ko) 2017-10-11
EP2646500B1 (de) 2014-09-03
TWI581948B (zh) 2017-05-11
AU2011336966A1 (en) 2013-04-04
US9902118B2 (en) 2018-02-27
US20150091216A1 (en) 2015-04-02
CN103221459A (zh) 2013-07-24
ES2525170T3 (es) 2014-12-18
CA2817369A1 (en) 2012-06-07

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