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US20150084228A1 - Reinforced Hollow Profiles - Google Patents

Reinforced Hollow Profiles Download PDF

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Publication number
US20150084228A1
US20150084228A1 US14509821 US201414509821A US2015084228A1 US 20150084228 A1 US20150084228 A1 US 20150084228A1 US 14509821 US14509821 US 14509821 US 201414509821 A US201414509821 A US 201414509821A US 2015084228 A1 US2015084228 A1 US 2015084228A1
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Prior art keywords
fibers
profile
die
embodiments
fiber
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US14509821
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Sherri M. Nelson
David W. Eastep
Timothy A. Regan
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Ticona LLC
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Ticona LLC
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    • 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
    • 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
    • B29C70/06Fibrous reinforcements only
    • 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
    • B29B15/00Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00
    • B29B15/08Pretreatment of the material to be shaped, not covered by groups B29B7/00 - B29B13/00 of reinforcements or fillers
    • B29B15/10Coating or impregnating independently of the moulding or shaping step
    • B29B15/12Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length
    • B29B15/122Coating or impregnating independently of the moulding or shaping step of reinforcements of indefinite length with a matrix in liquid form, e.g. as melt, solution or latex
    • 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
    • B29C47/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C47/02Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor incorporating preformed parts or layers, e.g. extrusion moulding around inserts or for coating articles
    • 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
    • B29C47/00Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C47/04Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor of multilayered or multi-component, e.g. co-extruded layers or components or multicoloured articles or coloured articles
    • B29C47/06Multilayered articles or multi-component articles
    • 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
    • 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
    • B29C70/06Fibrous reinforcements only
    • B29C70/08Fibrous reinforcements only comprising combinations of different forms of fibrous reinforcements incorporated in matrix material, forming one or more layers, and with or without non-reinforced layers
    • 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
    • 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
    • B29C70/28Shaping operations therefor
    • B29C70/40Shaping or impregnating by compression not applied
    • B29C70/50Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC], cross moulding compounds [XMC]
    • B29C70/52Pultrusion, i.e. forming and compressing by continuously pulling through a die
    • 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
    • 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
    • B29C70/28Shaping operations therefor
    • B29C70/40Shaping or impregnating by compression not applied
    • B29C70/50Shaping or impregnating by compression not applied for producing articles of indefinite length, e.g. prepregs, sheet moulding compounds [SMC], cross moulding compounds [XMC]
    • B29C70/52Pultrusion, i.e. forming and compressing by continuously pulling through a die
    • B29C70/521Pultrusion, i.e. forming and compressing by continuously pulling through a die and impregnating the reinforcement before the die
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE, IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS
    • B29K2055/00Use of specific polymers obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of main groups B29K2023/00 -  B29K49/00, e.g. having a vinyl group, as moulding material
    • B29K2055/02ABS polymers, i.e. acrylonitrile-butadiene-styrene polymers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE, IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS
    • B29K2101/00Use of unspecified macromolecular compounds as moulding material
    • B29K2101/12Thermoplastic materials
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE, IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS
    • B29K2105/00Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/06Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts
    • B29K2105/08Condition, form or state of moulded material or of the material to be shaped containing reinforcements, fillers or inserts of continuous length, e.g. cords, rovings, mats, fabrics, strands, yarns
    • B29K2105/10Cords, strands or rovings, e.g. oriented cords, strands or rovings
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE, IN GENERAL
    • B29KINDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS
    • B29K2309/00Use of inorganic materials not provided for in groups B29K2303/00 - B29K2307/00, as reinforcement
    • B29K2309/08Glass
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE, IN GENERAL
    • B29LINDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2009/00Layered products
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B29WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE, IN GENERAL
    • B29LINDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2022/00Hollow articles
    • 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/13Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/131Glass, ceramic, or sintered, fused, fired, or calcined metal oxide or metal carbide containing [e.g., porcelain, brick, cement, etc.]
    • Y10T428/1314Contains fabric, fiber particle, or filament made of glass, ceramic, or sintered, fused, fired, or calcined metal oxide, or metal carbide or other inorganic compound [e.g., fiber glass, mineral fiber, sand, etc.]
    • 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/13Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/1372Randomly noninterengaged or randomly contacting fibers, filaments, particles, or flakes
    • 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/249921Web or sheet containing structurally defined element or component
    • Y10T428/249924Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
    • Y10T428/24994Fiber embedded in or on the surface of a polymeric matrix
    • 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/249921Web or sheet containing structurally defined element or component
    • Y10T428/249924Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
    • Y10T428/24994Fiber embedded in or on the surface of a polymeric matrix
    • Y10T428/249949Two or more chemically different fibers
    • 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/249921Web or sheet containing structurally defined element or component
    • Y10T428/249924Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
    • Y10T428/24994Fiber embedded in or on the surface of a polymeric matrix
    • Y10T428/24995Two or more layers

Abstract

A hollow lineal profile formed from a continuous fiber reinforced ribbon (“CFRT”) that contains a plurality of continuous fibers embedded within a first thermoplastic polymer matrix. To enhance the tensile strength of the profile, the continuous fibers are aligned within the ribbon in a substantially longitudinal direction (e.g., the direction of pultrusion). In addition to continuous fibers, the hollow profile of the present invention also contains a plurality of long fibers that may be optionally embedded within a second thermoplastic matrix to form a long fiber reinforced thermoplastic (“LFRT”). The long fibers may be incorporated into the continuous fiber ribbon or formed as a separate layer of the profile. Regardless, at least at a portion of the long fibers are oriented at an angle (e.g., 90°) to the longitudinal direction to provide increased transverse strength to the profile.

Description

    RELATED APPLICATIONS
  • [0001]
    The present application claims priority as a divisional application of U.S. patent application Ser. No. 13/698,375, filed on Feb. 12, 2013, which is a U.S. national stage filing of International Patent Application No. PCT/US2011/041445, filed on Jun. 22, 2011, which claims priority to Provisional Application Ser. No. 61/357,294, filed on Jun. 22, 2010, all of which are incorporated by reference in their entireties herein.
  • BACKGROUND OF THE INVENTION
  • [0002]
    Hollow profiles have been formed by pulling (“pultruding”) continuous fibers through a resin and then shaping the fiber-reinforced resin within a pultrusion die. Because the profiles have continuous fibers oriented in the machine direction (longitudinal), they often exhibit a high tensile strength in the machine direction. The transverse strength of such hollow profiles is, however, often poor, which can cause the material to split when a stress is applied in a cross-machine direction (transverse). In this regard, various attempts have been made to strengthen hollow profiles in the transverse direction. For example, U.S. Pat. No. 7,514,135 to Davies, et al. describes a hollow part formed by providing a first layer of reinforcing rovings extending in a longitudinal pultrusion direction and forming a second layer on the first layer, the second layer containing at least some reinforcing fibers that extend in the transverse direction. One problem with this method, however, it is that it relies upon a thermoset resin to help achieve the desired strength properties. Such resins are difficult to use during manufacturing and do not always possess good bonding characteristics for forming layers with other materials. Furthermore, the method described therein is also problematic in that it is difficult to apply the transverse fibers at selective locations (e.g., where they are needed).
  • [0003]
    As such, a need currently exists for a hollow profile that exhibits good transverse strength and that can be made in a relatively efficient and simple manner.
  • SUMMARY OF THE INVENTION
  • [0004]
    In accordance with one embodiment of the present invention, a hollow lineal profile is disclosed. The profile comprises a consolidated ribbon that contains a plurality of continuous fibers embedded within a first thermoplastic matrix and substantially oriented in a longitudinal direction. The profile also comprises a plurality of long fibers, at least a portion of which are oriented at an angle relative to the longitudinal direction. The ratio of the weight of the continuous fibers to the ratio of the weight of the long fibers is from about 0.2 to about 10. Further, the ratio of flexural modulus to the maximum flexural strength of the profile is from about 50 to about 2200.
  • [0005]
    In accordance with another embodiment of the present invention, a method for forming a pultruded hollow profile is disclosed. The method comprises impregnating a plurality of continuous fibers with a thermoplastic matrix within an extrusion device; consolidating the impregnated fibers to form a first ribbon in which the continuous fibers are oriented in a longitudinal direction; pultruding the first ribbon and at least a second ribbon through a die to form the hollow profile, wherein the first ribbon, the second ribbon, or both contain long fibers.
  • [0006]
    Other features and aspects of the present invention are set forth in greater detail below.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • [0007]
    A full and enabling disclosure of the present invention, including the best mode thereof to one skilled in the art, is set forth more particularly in the remainder of the specification, including reference to the accompanying figures, in which:
  • [0008]
    FIG. 1 is a schematic illustration of one embodiment of a pultrusion system that may be employed in the present invention;
  • [0009]
    FIG. 2 is a schematic illustration of one embodiment of an impregnation system for use in the present invention;
  • [0010]
    FIG. 3A is a cross-sectional view of the impregnation die shown in FIG. 2;
  • [0011]
    FIG. 3B is an exploded view of one embodiment of a manifold assembly and gate passage for an impregnation die that may be employed in the present invention;
  • [0012]
    FIG. 3C is a perspective view of one embodiment of a plate at least partially defining an impregnation zone that may be employed in the present invention;
  • [0013]
    FIG. 4 is a side view of one embodiment of pre-shaping and pultrusion dies that may be employed in the present invention, wherein the flow of the continuous and long fiber materials are illustrated as they pass through the dies;
  • [0014]
    FIG. 5 is a perspective view of the dies of FIG. 4;
  • [0015]
    FIG. 6 is a top view of one embodiment of a mandrel that may be employed in the present invention to shape the long fiber layer, wherein the flow of the long fiber material is also illustrated as it passes over the mandrel;
  • [0016]
    FIG. 7 is a perspective view of the mandrel section of FIG. 6;
  • [0017]
    FIG. 8 is an exploded perspective view of one embodiment of a mandrel section that may be employed in the present invention to shape the continuous fiber layer, wherein the flow of the continuous fiber material is also illustrated as it passes over the mandrel;
  • [0018]
    FIG. 9 is a perspective view of the mandrel section of FIG. 8;
  • [0019]
    FIGS. 10A and 10B are other perspective views of the mandrel section of FIG. 8, in which FIG. 10A shows a right perspective view and FIG. 10B shows a left perspective view of the mandrel section;
  • [0020]
    FIG. 11 is a cross-sectional view of one embodiment of a rectangular, hollow profile of the present invention;
  • [0021]
    FIG. 12 is a cross-sectional view of another embodiment of a rectangular, hollow profile of the present invention;
  • [0022]
    FIG. 13 is side view of one embodiment of a pre-shaping and pultrusion die system that may be employed to form the profile of FIG. 12;
  • [0023]
    FIG. 14 is perspective view of the pre-shaping and pultrusion die system of FIG. 13;
  • [0024]
    FIG. 15 is a cross-sectional view of another embodiment of a rectangular, hollow profile of the present invention;
  • [0025]
    FIG. 16 is a cross-sectional view of one embodiment of an L-shaped, hollow profile of the present invention; and
  • [0026]
    FIG. 17 is yet another embodiment of a rectangular, hollow profile of the present invention.
  • [0027]
    Repeat use of reference characters in the present specification and drawings is intended to represent the same or analogous features or elements of the present invention.
  • DETAILED DESCRIPTION OF REPRESENTATIVE EMBODIMENTS Definitions
  • [0028]
    As used herein, the term “profile” generally refers to a pultruded part. The profile may possess a wide variety of cross-sectional shapes, such as square, rectangular, circular, elliptical, triangular, I-shaped, C-shaped, U-shaped, J-shaped, L-shaped, slotted, etc. Such profiles may be employed as a structural member for window lineals, decking planks, railings, balusters, roofing tiles, siding, trim boards, pipe, fencing, posts, light posts, highway signage, roadside marker posts, etc.
  • [0029]
    As used herein, the term “hollow” generally means that at least a portion of the interior of the profile is a voided space. The voided space may optionally extend the entire the length of the profile.
  • [0030]
    As used herein, the term “continuous fibers” generally refers to fibers, filaments, yarns, or rovings (e.g., bundles of fibers) having a length that is generally limited only by the length of the part. For example, such fibers may have a length greater than about 25 millimeters, in some embodiments about 50 millimeters or more, and in some embodiments, about 100 millimeters or more.
  • [0031]
    As used herein, the term “long fibers” generally refers to fibers, filaments, yarns, or rovings that are not continuous and typically have a length of from about 0.5 to about 25 millimeters, in some embodiments, from about 0.8 to about 15 millimeters, and in some embodiments, from about 1 to about 12 millimeters.
  • DETAILED DESCRIPTION
  • [0032]
    It is to be understood by one of ordinary skill in the art that the present discussion is a description of exemplary embodiments only, and is not intended as limiting the broader aspects of the present invention.
  • [0033]
    Generally speaking, the present invention is directed to a hollow lineal profile formed from a continuous fiber reinforced ribbon (“CFRT”) that contains a plurality of continuous fibers embedded within a first thermoplastic polymer matrix. To enhance the tensile strength and modulus of the profile, the continuous fibers are aligned within the ribbon in a substantially longitudinal direction (e.g., the direction of pultrusion). In addition to continuous fibers, the hollow profile of the present invention also contains a plurality of long fibers that may be optionally embedded within a second thermoplastic matrix to form a long fiber reinforced thermoplastic (“LFRT”). The long fibers may be incorporated into the continuous fiber ribbon or formed as a separate layer of the profile. Regardless, at least a portion of the long fibers are oriented at an angle (e.g., 90°) relative to the longitudinal direction to provide increased transverse strength to the profile.
  • [0034]
    To achieve a good balance between tensile strength and transverse strength, the present inventors have discovered that the relative proportion of the continuous and long fibers may be selectively controlled. Namely, the ratio of the weight of continuous fibers to the weight of long fibers is within the range of from about 0.2 to about 10, in some embodiments from about 0.4 to about 5, and in some embodiments, from about 0.5 to about 4. For instance, continuous fibers may constitute from about 10 wt. % to about 90 wt. %, in some embodiments from about 20 wt. % to about 70 wt. %, and in some embodiments, from about 30 wt. % to about 60 wt. % of the profile. Likewise, long fibers may constitute from about 0.5 wt. % to about 50 wt. %, in some embodiments from about 1 wt. % to about 40 wt. %, and in some embodiments, from about 2 wt. % to about 30 wt. % of the profile.
  • [0035]
    The resulting hollow profiles of the present invention may therefore exhibit a relatively high maximum flexural strength (in the transverse direction) in comparison to profiles having the same shape and size, but lacking the long fiber reinforcement of the present invention. For example, the maximum flexural strength (also known as the modulus of rupture or bend strength) may be about 12 Megapascals (“MPa”) or more, in some embodiments from about 15 to about 50 MPa, and in some embodiments, from about 20 to about 40 MPa. The term “maximum flexural strength” generally refers to the maximum stress reached on a stress-strain curve produced by a “three point flexural” test (such as ASTM D790-10, Procedure A or ISO 178) in the transverse direction at room temperature. It represents the ability of the material to withstand an applied stress in the transverse direction to failure. Likewise, the profile may also exhibit a high flexural modulus. The term “flexural modulus” generally refers to the ratio of stress to strain in flexural deformation (units of force per area), or the tendency for a material to bend. It is determined from the slope of a stress-strain curve produced by a “three point flexural” test (such as ASTM D790-10, Procedure A or ISO 178). For example, the profile of the present invention may exhibit a flexural modulus of about 2 Gigapascals (“GPa) or more, in some embodiments from about 2 to about 25 GPa, in some embodiments from about 4 to about 20 GPa, and in some embodiments, from about 5 to about 15 GPa.
  • [0036]
    The actual values for modulus and strength may of course vary depending on the desired application. Nevertheless, the ratio of the flexural modulus to the maximum flexural strength typically falls within a certain range to achieve a part that exhibits a balance between tensile strength and modulus properties, as well as transverse strength. This ratio, for example, typically ranges from about 50 to about 2200, in some embodiments from about 100 to about 1000, in some embodiments from about 200 to about 800, and in some embodiments, from about 250 to about 600.
  • [0037]
    The profile may also have a very low void fraction, such as about 3% or less, in some embodiments about 2% or less, and in some embodiments, about 1% or less. The void fraction may be determined in the manner described above, such as using a “resin burn off” test in accordance with ASTM D 2584-08.
  • [0038]
    The continuous fibers employed in the hollow profile of the present invention may be formed from any conventional material known in the art, such as metal fibers; glass fibers (e.g., E-glass, A-glass, C-glass, D-glass, AR-glass, R-glass, S1-glass, S2-glass), carbon fibers (e.g., graphite), boron fibers, ceramic fibers (e.g., alumina or silica), aramid fibers (e.g., Kevlar) marketed by E. I. duPont de Nemours, Wilmington, Del.), synthetic organic fibers (e.g., polyamide, polyethylene, paraphenylene, terephthalamide, polyethylene terephthalate and polyphenylene sulfide), and various other natural or synthetic inorganic or organic fibrous materials known for reinforcing thermoplastic compositions. Glass fibers and carbon fibers are particularly desirable for use in the continuous fibers. Such fibers often have a nominal diameter of about 4 to about 35 micrometers, and in some embodiments, from about 9 to about 35 micrometers. The fibers may be twisted or straight. If desired, the fibers may be in the form of rovings (e.g., bundle of fibers) that contain a single fiber type or different types of fibers. Different fibers may be contained in individual rovings or, alternatively, each roving may contain a different fiber type. For example, in one embodiment, certain rovings may contain continuous carbon fibers, while other rovings may contain glass fibers. The number of fibers contained in each roving can be constant or vary from roving to roving. Typically, a roving may contain from about 1,000 fibers to about 50,000 individual fibers, and in some embodiments, from about 2,000 to about 40,000 fibers.
  • [0039]
    Any of a variety of thermoplastic polymers may also be employed to form the first thermoplastic matrix in which the continuous fibers are embedded. Suitable thermoplastic polymers for use in the present invention may include, for instance, polyolefins (e.g., polypropylene, propylene-ethylene copolymers, etc.), polyesters (e.g., polybutylene terephalate (“PBT”)), polycarbonates, polyamides (e.g., Nylon™), polyether ketones (e.g., polyetherether ketone (“PEEK”)), polyetherimides, polyarylene ketones (e.g., polyphenylene diketone (“PPDK”)), liquid crystal polymers, polyarylene sulfides (e.g., polyphenylene sulfide (“PPS”)), fluoropolymers (e.g., polytetrafluoroethylene-perfluoromethylvinylether polymer, perfluoro-alkoxyalkane polymer, petrafluoroethylene polymer, ethylene-tetrafluoroethylene polymer, etc.), polyacetals, polyurethanes, polycarbonates, styrenic polymers (e.g., acrylonitrile butadiene styrene (“ABS”)), and so forth. Polypropylene is a particularly suitable thermoplastic polymer.
  • [0040]
    The continuous fiber ribbon is generally formed in a manner to minimize its void fraction and ensure good impregnation. In this regard, an extrusion device may be employed in the present invention to embed the continuous fibers into a thermoplastic matrix. Among other things, the extrusion device facilitates the ability of the thermoplastic polymer to be applied to the entire surface of the fibers. For instance, the void fraction may be about 3% or less, in some embodiments about 2% or less, and in some embodiments, about 1% or less. The void fraction may be measured using techniques well known to those skilled in the art. For example, the void fraction may be measured using a “resin burn off” test in which samples are placed in an oven (e.g., at 600° C. for 3 hours) to burn out the resin. The mass of the remaining fibers may then be measured to calculate the weight and volume fractions.
  • [0041]
    Such “burn off” testing may be performed in accordance with ASTM D 2584-08 to determine the weights of the fibers and the thermoplastic matrix, which may then be used to calculate the “void fraction” based on the following equations:
  • [0000]

    V f=100*(ρt−ρc)/ρt
  • [0000]
    where,
  • [0042]
    Vf is the void fraction as a percentage;
  • [0043]
    ρc is the density of the composite as measured using known techniques, such as with a liquid or gas pycnometer (e.g., helium pycnometer);
  • [0044]
    ρt is the theoretical density of the composite as is determined by the following equation:
  • [0000]

    ρt=1/[W ff +W mm]
  • [0045]
    ρm is the density of the thermoplastic matrix (e.g., at the appropriate crystallinity);
  • [0046]
    ρf is the density of the fibers;
  • [0047]
    Wf is the weight fraction of the fibers; and
  • [0048]
    Wm is the weight fraction of the thermoplastic matrix.
  • [0049]
    Alternatively, the void fraction may be determined by chemically dissolving the resin in accordance with ASTM D 3171-09. The “burn off” and “dissolution” methods are particularly suitable for glass fibers, which are generally resistant to melting and chemical dissolution. In other cases, however, the void fraction may be indirectly calculated based on the densities of the thermoplastic polymer, fibers, and ribbon in accordance with ASTM D 2734-09 (Method A), where the densities may be determined ASTM D792-08 Method A. Of course, the void fraction can also be estimated using conventional microscopy equipment.
  • [0050]
    Referring to FIG. 2, one embodiment of an extrusion device is shown that may be employed for impregnating the fibers with a thermoplastic polymer. More particularly, the apparatus includes an extruder 120 containing a screw shaft 124 mounted inside a barrel 122. A heater 130 (e.g., electrical resistance heater) is mounted outside the barrel 122. During use, a thermoplastic polymer feedstock 127 is supplied to the extruder 120 through a hopper 126. The thermoplastic feedstock 127 is conveyed inside the barrel 122 by the screw shaft 124 and heated by frictional forces inside the barrel 122 and by the heater 130. Upon being heated, the feedstock 127 exits the barrel 122 through a barrel flange 128 and enters a die flange 132 of an impregnation die 150.
  • [0051]
    A continuous fiber roving 142 or a plurality of continuous fiber rovings 142 are supplied from a reel or reels 144 to die 150. The rovings 142 are generally kept apart a certain distance before impregnation, such as at least about 4 millimeters, and in some embodiments, at least about 5 millimeters. The feedstock 127 may further be heated inside the die by heaters 133 mounted in or around the die 150. The die is generally operated at temperatures that are sufficient to cause melting and impregnation of the thermoplastic polymer. Typically, the operation temperatures of the die is higher than the melt temperature of the thermoplastic polymer, such as at temperatures from about 200° C. to about 450° C. When processed in this manner, the continuous fiber rovings 142 become embedded in the polymer matrix, which may be a resin 214 (FIG. 3A) processed from the feedstock 127. The mixture is then extruded from the impregnation die 150 to create an extrudate 152.
  • [0052]
    A pressure sensor 137 (FIG. 3A) senses the pressure near the impregnation die 150 to allow control to be exerted over the rate of extrusion by controlling the rotational speed of the screw shaft 124, or the federate of the feeder. That is, the pressure sensor 137 is positioned near the impregnation die 150 so that the extruder 120 can be operated to deliver a correct amount of resin 214 for interaction with the fiber rovings 142. After leaving the impregnation die 150, the extrudate 152, or impregnated fiber rovings 142, may enter an optional pre-shaping, or guiding section (not shown) before entering a nip formed between two adjacent rollers 190. Although optional, the rollers 190 can help to consolidate the extrudate 152 into the form of a ribbon (or tape), as well as enhance fiber impregnation and squeeze out any excess voids. In addition to the rollers 190, other shaping devices may also be employed, such as a die system. The resulting consolidated ribbon 156 is pulled by tracks 162 and 164 mounted on rollers. The tracks 162 and 164 also pull the extrudate 152 from the impregnation die 150 and through the rollers 190. If desired, the consolidated ribbon 156 may be wound up at a section 171. Generally speaking, the ribbons are relatively thin and typically have a thickness of from about 0.05 to about 1 millimeter, in some embodiments from about 0.1 to about 0.8 millimeters, and in some embodiments, from about 0.2 to about 0.4 millimeters.
  • [0053]
    Within the impregnation die, it is generally desired that the rovings 142 are traversed through an impregnation zone 250 to impregnate the rovings with the polymer resin 214. In the impregnation zone 250, the polymer resin may be forced generally transversely through the rovings by shear and pressure created in the impregnation zone 250, which significantly enhances the degree of impregnation. This is particularly useful when forming a composite from ribbons of a high fiber content, such as about 35% weight fraction (“Wf”) or more, and in some embodiments, from about 40% Wf or more. Typically, the die 150 will include a plurality of contact surfaces 252, such as for example at least 2, at least 3, from 4 to 7, from 2 to 20, from 2 to 30, from 2 to 40, from 2 to 50, or more contact surfaces 252, to create a sufficient degree of penetration and pressure on the rovings 142. Although their particular form may vary, the contact surfaces 252 typically possess a curvilinear surface, such as a curved lobe, rod, etc. The contact surfaces 252 are also typically made of a metal material.
  • [0054]
    FIG. 3A shows a cross-sectional view of an impregnation die 150. As shown, the impregnation die 150 includes a manifold assembly 220, a gate passage 270, and an impregnation zone 250. The manifold assembly 220 is provided for flowing the polymer resin 214 therethrough. For example, the manifold assembly 220 may include a channel 222 or a plurality of channels 222. The resin 214 provided to the impregnation die 150 may flow through the channels 222.
  • [0055]
    As shown in FIG. 3B, some portions of the channels 222 may be curvilinear, and in exemplary embodiments, the channels 222 have a symmetrical orientation along a central axis 224. Further, in some embodiments, the channels may be a plurality of branched runners 222, which may include first branched runner group 232, second group 234, third group 236, and, if desired, more branched runner groups. Each group may include 2, 3, 4 or more runners 222 branching off from runners 222 in the preceding group, or from an initial channel 222.
  • [0056]
    The branched runners 222 and the symmetrical orientation thereof generally evenly distribute the resin 214, such that the flow of resin 214 exiting the manifold assembly 220 and coating the rovings 142 is substantially uniformly distributed on the rovings 142. This desirably allows for generally uniform impregnation of the rovings 142.
  • [0057]
    Further, the manifold assembly 220 may in some embodiments define an outlet region 242, which generally encompasses at least a downstream portion of the channels or runners 222 from which the resin 214 exits. In some embodiments, at least a portion of the channels or runners 222 disposed in the outlet region 242 have an increasing area in a flow direction 244 of the resin 214. The increasing area allows for diffusion and further distribution of the resin 214 as the resin 214 flows through the manifold assembly 220, which further allows for substantially uniform distribution of the resin 214 on the rovings 142.
  • [0058]
    As further illustrated in FIGS. 3A and 3B, after flowing through the manifold assembly 220, the resin 214 may flow through gate passage 270. Gate passage 270 is positioned between the manifold assembly 220 and the impregnation zone 250, and is provided for flowing the resin 214 from the manifold assembly 220 such that the resin 214 coats the rovings 142. Thus, resin 214 exiting the manifold assembly 220, such as through outlet region 242, may enter gate passage 270 and flow therethrough, as shown.
  • [0059]
    Upon exiting the manifold assembly 220 and the gate passage 270 of the die 150 as shown in FIG. 3A, the resin 214 contacts the rovings 142 being traversed through the die 150. As discussed above, the resin 214 may substantially uniformly coat the rovings 142, due to distribution of the resin 214 in the manifold assembly 220 and the gate passage 270. Further, in some embodiments, the resin 214 may impinge on an upper surface of each of the rovings 142, or on a lower surface of each of the rovings 142, or on both an upper and lower surface of each of the rovings 142. Initial impingement on the rovings 142 provides for further impregnation of the rovings 142 with the resin 214.
  • [0060]
    As shown in FIG. 3A, the coated rovings 142 are traversed in run direction 282 through impregnation zone 250, which is configured to impregnate the rovings 142 with the resin 214. For example, as shown in FIGS. 3A and 3C, the rovings 142 are traversed over contact surfaces 252 in the impregnation zone.
  • [0061]
    Impingement of the rovings 142 on the contact surface 252 creates shear and pressure sufficient to impregnate the rovings 142 with the resin 214 coating the rovings 142.
  • [0062]
    In some embodiments, as shown in FIG. 3A, the impregnation zone 250 is defined between two spaced apart opposing plates 256 and 258. First plate 256 defines a first inner surface 257, while second plate 258 defines a second inner surface 259. The contact surfaces 252 may be defined on or extend from both the first and second inner surfaces 257 and 259, or only one of the first and second inner surfaces 257 and 259. FIG. 3C illustrates the second plate 258 and the various contact surfaces thereon that form at least a portion of the impregnation zone 250 according to these embodiments. In exemplary embodiments, as shown in FIG. 3A, the contact surfaces 252 may be defined alternately on the first and second surfaces 257 and 259 such that the rovings alternately impinge on contact surfaces 252 on the first and second surfaces 257 and 259. Thus, the rovings 142 may pass contact surfaces 252 in a waveform, tortuous or sinusoidual-type pathway, which enhances shear.
  • [0063]
    The angle 254 at which the rovings 142 traverse the contact surfaces 252 may be generally high enough to enhance shear, but not so high to cause excessive forces that will break the fibers. Thus, for example, the angle 254 may be in the range between approximately 1° and approximately 30°, and in some embodiments, between approximately 5° and approximately 25°.
  • [0064]
    In alternative embodiments, the impregnation zone 250 may include a plurality of pins (not shown), each pin having a contact surface 252. The pins may be static, freely rotational, or rotationally driven. In further alternative embodiments, the contact surfaces 252 and impregnation zone 250 may comprise any suitable shapes and/or structures for impregnating the rovings 142 with the resin 214 as desired or required.
  • [0065]
    To further facilitate impregnation of the rovings 142, they may also be kept under tension while present within the impregnation die. The tension may, for example, range from about 5 to about 300 Newtons, in some embodiments from about 50 to about 250 Newtons, and in some embodiments, from about 100 to about 200 Newtons per roving 142 or tow of fibers.
  • [0066]
    As shown in FIG. 3A, in some embodiments, a land zone 280 may be positioned downstream of the impregnation zone 250 in run direction 282 of the rovings 142. The rovings 142 may traverse through the land zone 280 before exiting the die 150. As further shown in FIG. 3A, in some embodiments, a faceplate 290 may adjoin the impregnation zone 250. Faceplate 290 is generally configured to meter excess resin 214 from the rovings 142. Thus, apertures in the faceplate 290, through which the rovings 142 traverse, may be sized such that when the rovings 142 are traversed therethrough, the size of the apertures causes excess resin 214 to be removed from the rovings 142.
  • [0067]
    The impregnation die shown and described above is but one of various possible configurations that may be employed in the present invention. In alternative embodiments, for example, the fibers may be introduced into a crosshead die that is positioned at an angle relative to the direction of flow of the polymer melt. As the fibers move through the crosshead die and reach the point where the polymer exits from an extruder barrel, the polymer is forced into contact with the fibers. It should also be understood that any other extruder design may also be employed, such as a twin screw extruder. Still further, other components may also be optionally employed to assist in the impregnation of the fibers. For example, a “gas jet” assembly may be employed in certain embodiments to help uniformly spread a bundle or tow of individual fibers, which may each contain up to as many as 24,000 fibers, across the entire width of the merged tow. This helps achieve uniform distribution of strength properties in the ribbon. Such an assembly may include a supply of compressed air or another gas that impinges in a generally perpendicular fashion on the moving fiber tows that pass across the exit ports. The spread fiber bundles may then be introduced into a die for impregnation, such as described above.
  • [0068]
    Regardless of the technique employed, the continuous fibers are oriented in the longitudinal direction (the machine direction “A” of the system of FIG. 1) to enhance tensile strength. Besides fiber orientation, other aspects of the ribbon and pultrusion process are also controlled to achieve the desired strength. For example, a relatively high percentage of continuous fibers may be employed in the ribbon to provide enhanced strength properties. For instance, continuous fibers typically constitute from about 40 wt. % to about 90 wt. %, in some embodiments from about 50 wt. % to about 85 wt. %, and in some embodiments, from about 55 wt. % to about 75 wt. % of the ribbon. Likewise, thermoplastic polymer(s) typically constitute from about 10 wt. % to about 60 wt. %, in some embodiments from about 15 wt. % to about 50 wt. %, and in some embodiments, from about 25 wt. % to about 45 wt. % of the ribbon.
  • [0069]
    Furthermore, a combination of multiple continuous fibers ribbons may be employed that are laminated together to form a strong, integrated structure having the desired thickness. The number of ribbons employed may vary based on the desired thickness and strength of the profile, as well as the nature of the ribbons themselves. In most cases, however, the number of ribbons is from 2 to 40, in some embodiments from 3 to 30, and in some embodiments, from 4 to 25.
  • [0070]
    As stated above, the hollow profile also contains a plurality of long fibers optionally embedded within a second thermoplastic matrix. The long fibers may be formed from any of the material, shape, and/or size as described above with respect to the continuous fibers. Glass fibers and carbon fibers are particularly desirable for use as the long fibers. Furthermore, the second thermoplastic matrix in which the long fibers may optionally be embedded may include a thermoplastic polymer, such as described above. It should be understood that the first thermoplastic matrix employed for the continuous fibers may be the same or different than the second thermoplastic matrix employed for the long fibers. In one embodiment, for example, the long fibers are separately impregnated with a thermoplastic polymer, such as in a manner described below, and thereafter cooled and chopped into to pellets having a length of about 25 millimeters or less. These pellets may be subsequently combined with a continuous fiber ribbon. Regardless, at least a portion of the long fibers in the hollow profile are oriented at an angle relative to the longitudinal direction (i.e., pultrusion direction) to provide increased transverse strength. For example, about 10% or more, in some embodiments about 20% or more, and in some embodiments, about 30% or more of the fibers may be oriented at an angle relative to the longitudinal direction. This angle may, for instance, be about 10° to about 120°, in some embodiments from about 20° to about 110° C., and in one embodiment, about 90°. This may be accomplished by intentionally orienting the fibers in the desired direction, or by random distribution.
  • [0071]
    The manner in which the long fibers and the continuous fiber ribbon are combined together to form the hollow profile of the present invention may vary depending on the intended application and the locations of the profile in which increased strength is required. In one embodiment, for example, the long fiber material is formed as a separate layer from the continuous fiber ribbon. Among other things, this allows the long fiber material to be selectively added at only those locations where increased transverse strength is most needed.
  • [0072]
    Referring to FIG. 1, one particular embodiment of a system is shown in which one or more continuous fiber ribbons 12 are initially provided in a wound package on a creel 20. The creel 20 may be an unreeling creel that includes a frame provided with horizontal rotating spindles 22, each supporting a package. A pay-out creel may also be employed, particularly if desired to induce a twist into the fibers. It should also be understood that the ribbons may also be formed in-line with the formation of the profile. In one embodiment, for example, the extrudate 152 exiting the impregnation die 150 from FIG. 2 may be directly supplied to the system used to form a profile. A tension-regulating device 40 may also be employed to help control the degree of tension in the ribbons 12. The device 40 may include inlet plate 30 that lies in a vertical plane parallel to the rotating spindles 22 of the creel 20. The tension-regulating device 40 may contain cylindrical bars 41 arranged in a staggered configuration so that the ribbons 12 passes over and under these bars to define a wave pattern. The height of the bars can be adjusted to modify the amplitude of the wave pattern and control tension.
  • [0073]
    If desired, the ribbons 12 may be heated in an oven 45 having any of a variety of known configuration, such as an infrared oven, convection oven, etc. During heating, the fibers are unidirectionally oriented to optimize the exposure to the heat and maintain even heat across the entire profile. The temperature to which the ribbons 12 are heated is generally high enough to soften the thermoplastic polymer to an extent that the ribbons can bond together. However, the temperature is not so high as to destroy the integrity of the material. The temperature may, for example, range from about 100° C. to about 300° C., in some embodiments from about 110° C. to about 275° C., and in some embodiments, from about 120° C. to about 250° C. In one particular embodiment, for example, acrylonitrile-butadiene-styrene (ABS) is used as the polymer, and the ribbons are heated to or above the melting point of ABS, which is about 105° C. In another embodiment, polybutylene terephalate (PBT) is used as the polymer, and the ribbons are heated to or above the melting point of PBT, which is about 224° C.
  • [0074]
    Upon being heated, the continuous fiber ribbons 12 may be provided to a consolidation die to help bond together different ribbon layers, as well as for alignment and formation of the initial shape of the profile. Referring to FIGS. 1, 4, and 5, for example, one embodiment of a consolidation die 50 for use in forming a “hollow” profile is shown in more detail. Although referred to herein as a single die, it should be understood that the consolidation die 50 may in fact be formed from multiple individual dies (e.g., face plate dies). In this particular embodiment, the consolidation die 50 receives a first layer (or laminate) 12 a of continuous fiber ribbons and a second layer (or laminate) 12 b of continuous fiber ribbons at an inlet end 56. The ribbons within each layer are bonded together and guided through channels (not shown) of the die 50 in a direction “A”. The channels may be provided in any of a variety of orientations and arrangements to result in the desired reinforcement scheme. In the illustrated embodiment, for example, the layers 12 a and 12 b are initially spaced apart from each other in the vertical direction. As they pass through the channels of the die 50, the widths of the layers 12 a and/or 12 b are optionally ribbonred to help prevent pressure wedges, and to keep the continuous fibers aligned and twist-free. Within the die 50, the ribbons are generally maintained at a temperature at or above the melting point of the thermoplastic matrix used in the ribbon to ensure adequate consolidation.
  • [0075]
    Although not specifically shown in FIGS. 1, 4, and 5, a mandrel may also be provided in the interior of the consolidation die 50 to help guide the laminates 12 a and 12 b into contact with each other on at least one side of the profile. In the illustrated embodiment, for example, a side portion 57 of the first layer 12 a and a side portion 53 of the second layer 12 b are angled so that they contact each other and form a side of the hollow profile. The other side of the profile is, however, typically left open within the consolidation die 50 so that the discontinuous fiber material can be subsequently applied to the interior of the profile in the pultrusion die. Of course, for those embodiments in which the discontinuous fiber material is not applied to the interior of the hollow profile, the consolidation die 50 may not be employed at all as the entire profile can be optionally shaped within the pultrusion die.
  • [0076]
    When in the desired position, the layers 12 a and 12 b of continuous fiber material are pulled into a pultrusion die 60. It is generally desired that the layers are allowed to cool briefly after exiting the consolidation die 50 and before entering the pultrusion die 60. This allows the consolidated laminate to retain its initial shape before progressing further through the system. Such cooling may be accomplished by simply exposing the layers to the ambient atmosphere (e.g., room temperature) or through the use of active cooling techniques (e.g., water bath or air cooling) as is known in the art. In one embodiment, for example, air is blown onto the layers (e.g., with an air ring). The cooling between these stages, however, generally occurs over a small period of time to ensure that the layers are still soft enough to be further shaped. For example, after exiting the consolidation die 50, the layers may be exposed to the ambient environment for only from about 1 to about 20 seconds, and in some embodiments, from about 2 to about 10 seconds, before entering the second die 60.
  • [0077]
    The configuration of the pultrusion die 60 depends in part on the desired shape and properties for the resulting profile. For hollow profiles, for example, the pultrusion die often contains a mandrel within its interior so that the fiber material flows between the interior surface of the die and the external surface of the mandrel to form the desired shape. Solid profiles, however, are typically formed without a mandrel. Further, although referred to herein as a single die, it should be understood that the pultrusion die 60 may be formed from multiple individual dies. In fact, the pultrusion die may preferably employ a first die section in which the discontinuous material is supplied and shaped a second die section in which the continuous fiber material is shaped. In FIGS. 4-5, for example, a first die section 62 is employed that supplies and shapes discontinuous fiber material 61 and a second die section 64 is employed that shapes the continuous fiber layers 12 a and 12 b.
  • [0078]
    The particular manner in which the long fiber material 61 is supplied to the first die section 62 is shown in more detail in FIGS. 6-8. As shown, a long fiber material 61 enters the first die section 62 and is curved into its interior cavity. Although not required, such a curved inlet allows the long fiber material 61 to gradually flow into in the direction “A” and toward a die outlet 67. In such embodiments, the angle β at which the long fiber material is provided relative to the flow direction “A” of the continuous fiber layers 12 a and 12 b may generally vary, but is typically about 45° or more, in some embodiments about 60° or more, and in some embodiments, from about 75° to about 90°. In certain cases, a non-perpendicular flow angle may be advantageous because it minimizes or overcomes backpressure in the die that may be caused by the high pressure flow of the long fiber material, which can sometimes lead to an undesirable backflow. The angled input orientation of the long fiber material, in combination with its curved configuration, may also reduce the likelihood that static spots (dead spots) may form inside the die, which may cause resin degradation, fiber hang-up, or breakage.
  • [0079]
    Upon entering the first die section 62, the discontinuous material 61 also flows over a mandrel 68. The mandrel 68 may be supported in a cantilever manner so that it resists the forward force of the continuous material being pulled around and over the mandrel. Further, although the entire mandrel is not shown herein, it should be understood that it may nevertheless extend into the aforementioned consolidation die 50 to help “pre-shape” the continuous fiber material in the manner described above. Regardless, the mandrel 68 shown in FIGS. 6-8 possesses multiple sections for accomplishing the desired shaping of the profile. More particularly, the mandrel 68 contains a first mandrel section 69 that is solid and generally rectangular in cross-section. Thus, the discontinuous material 61 passes over and around the mandrel section 69 from its proximal end 71 to its distal end 73. In doing so, the material 61 assumes the shape defined between the interior surface of the first die section 62 and an external surface 75 of the mandrel section 69, which in this embodiment, is a hollow rectangular shape.
  • [0080]
    The final shape of the continuous fiber layer is formed in the second die section 64 of the pultrusion die 60, over and around a second section 79 of the mandrel 68 as shown in FIGS. 9-10. The second mandrel section 79 contains a U-shaped recess 103 that engages a protrusion 77 of the first mandrel section 69 for connecting thereto. In this embodiment, the second mandrel section 79 also contains an upper wall 83 and lower wall 85 that are generally perpendicular to the direction “A” of material flow. An upwardly facing surface 91 intersects a curved edge 93 of the upper wall 83 and slopes axially in the direction “A”. Similarly, a downwardly facing surface 95 intersects a curved edge of the lower wall 85 and slopes axially in the direction “A”. The surfaces 91 and 95 both converge at an edge 97. During formation of the profile, the first layer 12 a of continuous fiber material is pulled over the surface 91 and assumes the shape defined between an interior surface of the pultrusion die 60 and the upper wall 83. The second layer 12 b of continuous fiber material is pulled over the surface 95 and likewise assumes the shape defined between an interior surface of the pultrusion die 60 and the lower wall 85. The layer 12 a and 12 b are also gradually pulled into contact with each other at the edge 97 to form one side of the resulting profile. If necessary, the materials may be subjected to a subsequent compression step, such as in a land die section (not shown), to further increase the degree of adhesion between the layers at their edges.
  • [0081]
    Within the die 60, the ribbons are generally maintained at a temperature well above the melting point of the thermoplastic matrix used in the ribbon to facilitate the ability to shape the part and intermix together the discontinuous fiber material. However, the temperature is not so high as to destroy the integrity of the material. The temperature may, for example, range from about 100° C. to about 350° C., in some embodiments from about 120° C. to about 320° C., and in some embodiments, from about 150° C. to about 300° C.
  • [0082]
    If desired, the resulting profile may also be applied with a capping layer to enhance the aesthetic appeal of the profile and/or protect it from environmental conditions. Referring to FIG. 1, for example, such a capping layer may be applied via an extruder oriented at any desired angle to introduce a thermoplastic resin into a capping die 72. The resin may contain any suitable thermoplastic polymer known in the art that is generally compatible with the thermoplastic polymer used to form the profile. Suitable capping polymers may include, for instance, acrylic polymers, polyvinyl chloride (PVC), polybutylene terephthalate (PBT), ABS, polyolefins, polyesters, polyacetals, polyamids, polyurethanes, etc. Although the capping resin is generally free of fibers, it may nevertheless contain other additives for improving the final properties of the profile. Additive materials employed at this stage may include those that are not suitable for incorporating into the continuous fiber or long fiber layers. For instance, it may be desirable to add pigments to the composite structure to reduce finishing labor of shaped articles, or it may be desirable to add flame retardant agents to the composite structure to enhance the flame retarding features of the shaped article. Because many additive materials are heat sensitive, an excessive amount of heat may cause them to decompose and produce volatile gases. Therefore, if a heat sensitive additive material is extruded with an impregnation resin under high heating conditions, the result may be a complete degradation of the additive material. Additive materials may include, for instance, mineral reinforcing agents, lubricants, flame retardants, blowing agents, foaming agents, ultraviolet light resistant agents, thermal stabilizers, pigments, and combinations thereof. Suitable mineral reinforcing agents may include, for instance, calcium carbonate, silica, mica, clays, talc, calcium silicate, graphite, calcium silicate, alumina trihydrate, barium ferrite, and combinations thereof.
  • [0083]
    While not shown in detail herein, the capping die 72 may include various features known in the art to help achieve the desired application of the capping layer. For instance, the capping die 72 may include an entrance guide that aligns the incoming profile. The capping die may also include a heating mechanism (e.g., heated plate) that pre-heats the profile before application of the capping layer to help ensure adequate bonding.
  • [0084]
    Following optional capping, the shaped part 15 is then finally cooled using a cooling system 80 as is known in the art. The cooling system 80 may, for instance, be a vacuum sizer that includes one or more blocks (e.g., aluminum blocks) that completely encapsulate the profile while a vacuum pulls the hot shape out against its walls as it cools. A cooling medium may be supplied to the sizer, such as air or water, to solidify the profile in the correct shape.
  • [0085]
    Vacuum sizers are typically employed when forming the profile. Even if a vacuum sizer is not employed, however, it is generally desired to cool the profile after it exits the capping die (or the consolidation or calibration die if capping is not applied). Cooling may occur using any technique known in the art, such a vacuum water tank, cool air stream or air jet, cooling jacket, an internal cooling channel, cooling fluid circulation channels, etc. Regardless, the temperature at which the material is cooled is usually controlled to achieve optimal mechanical properties, part dimensional tolerances, good processing, and an aesthetically pleasing composite. For instance, if the temperature of the cooling station is too high, the material might swell in the tool and interrupt the process. For semi-crystalline materials, too low of a temperature can likewise cause the material to cool down too rapidly and not allow complete crystallization, thereby jeopardizing the mechanical and chemical resistance properties of the composite. Multiple cooling die sections with independent temperature control can be utilized to impart the optimal balance of processing and performance attributes. In one particular embodiment, for example, a vacuum water tank is employed that is kept at a temperature of from about 10° C. to about 50° C., and in some embodiments, from about 15° C. to about 35° C.
  • [0086]
    As will be appreciated, the temperature of the profile as it advances through any section of the system of the present invention may be controlled to yield optimal manufacturing and desired final composite properties. Any or all of the assembly sections may be temperature controlled utilizing electrical cartridge heaters, circulated fluid cooling, etc., or any other temperature controlling device known to those skilled in the art.
  • [0087]
    Referring again to FIG. 1, a pulling device 82 is positioned downstream from the cooling system 80 that pulls the finished profile 16 through the system for final sizing of the composite. The pulling device 82 may be any device capable of pulling the profile through the process system at a desired rate. Typical pulling devices include, for example, caterpillar pullers and reciprocating pullers. If desired, one or more calibration dies (not shown) may also be employed. Such dies contain openings that are cut to the exact profile shape, graduated from oversized at first to the final profile shape. As the profile passes therethrough, any tendency for it to move or sag is counteracted, and it is pushed back (repeatedly) to its correct shape. Once sized, the profile may be cut to the desired length at a cutting station (not shown), such as with a cut-off saw capable of performing cross-sectional cuts.
  • [0088]
    One embodiment of the hollow profile formed from the method described above is shown in more detail in FIG. 11 as element 16. As illustrated, the hollow profile 16 has a generally rectangular shape. An inner layer 4 is formed by the LFRT material that extends around the entire profile and defines an interior surface 5. An outer layer 6 is likewise formed by the CFRT material that extends around the perimeter of the inner layer 4 and positioned adjacent thereto. The thickness of these layers and the relative proportion of the LFRT and CFRT materials may be strategically selected to help achieve a particular tensile strength and transverse strength (e.g., flexural modulus) for the profile. For example, higher percentages of LFRT material (and/or thickness) generally result in higher transverse strength, while higher percentages of CFRT material (and/or thickness) generally result in higher tensile strength. To optimize these properties, the ratio of the weight of the CFRT layer to the weight of the LFRT layer is typically from about 0.2 to about 10, in some embodiments from about 0.4 to about 5, and in some embodiments, from about 0.5 to about 4. In this regard, the thickness of the inner layer 4 may be from about 0.1 to about 2.0 millimeters, in some embodiments from about 0.5 to about 1.5 millimeters, and in some embodiments, from about 0.6 to about 1.2 millimeters, and the thickness of the outer layer 6 may be from about 0.2 to about 4.0 millimeters, in some embodiments from about 0.5 to about 3.0 millimeters, and in some embodiments, from about 1.0 to about 2.0 millimeters. The total thickness of the layers 4 and 6 may likewise be from about 1.0 to about 4.0 millimeters, and in some embodiments, from about 2.0 to about 3.0 millimeters.
  • [0089]
    The profile 16 of FIG. 11 also includes a capping layer 7 that extends around the perimeter of the outer layer 6 and defines an external surface 8 of the profile 16. The thickness of the capping layer 7 depends on the intended function of the part, but is typically from about 0.1 to about 5 millimeters, and in some embodiments, from about 0.2 to about 3 millimeters.
  • [0090]
    In the embodiments described and shown above, the LFRT material is positioned around substantially the entire interior perimeter of the profile. However, it should be understood that this is not required, and that it may be desired in certain applications to apply the material only to specific locations that are advantageous according to a particular design. One example of such a profile is shown in more detail in FIG. 12. As illustrated, the profile 216 generally has a hollow, rectangular shape. In this embodiment, an inner layer 206 is formed by the CFRT material that extends around the entire profile and defines an interior surface 205. The thickness of the layer 206 may be similar to the CFRT layer described above with reference to FIG. 11. Contrary to the embodiment of FIG. 11, however, the profile 216 does not contain a continuous LFRT layer. Instead, LFRT material is located at discrete layers 204 at upper and lower surfaces 208 and 209 of the profile 216. Such discrete placement of the LFRT material may provide enhanced transverse strength at only those locations where it is needed for a particular application. A capping layer 207 may cover the periphery of the profile 216.
  • [0091]
    FIGS. 13-14 illustrate one embodiment of the consolidation die 250 and pultrusion die 260 that may be employed to form the profile 216. Similar to the embodiments described above, the consolidation die 250 in this embodiment receives a first layer 212 a and second layer 212 b of continuous fiber material at an inlet end 256. The layers 212 a and 212 b are guided through channels (not shown) of the die 250 in a direction “A”. As they pass through the channels, the widths of the layers 212 a and/or 212 b are optionally ribbonred and connected at one side as described above. When in the desired position, the layers 212 a and 212 b are pulled into the pultrusion die 260, which employs a first die section 262, a second die section 264, and a mandrel 268 that extends therethrough. Together, each of these components helps shape the continuous fiber material. More particularly, as the continuous fiber layers pass over and around the mandrel 268 from its proximal to distal end, they assume the shape defined between the interior surface of the die 260 and an external surface of the mandrel, which in this embodiment, is a hollow rectangular shape. The long fiber material 281 is then introduced into a third die section 280 via an inlet portion, which is typically in the form of a cross-head die that extrudes the material at an input angle as mentioned above. In this particular embodiment, however, the long fiber material 281 is split into an upper stream 240 and a lower stream 242 within the third die section 280. As the streams 240 and 242 converge in the direction “A” of the material flow and are pulled through the die system, they form the upper and lower discrete layers 204, respectively, of the profile 216. A capping layer 207 may then be applied using a capping die 272 as shown.
  • [0092]
    Of course, other hollow profiles may be formed in the present invention. Referring to FIG. 15, for example, another embodiment of a generally rectangular, hollow profile 316 is shown in more detail. In this particular embodiment, an inner layer 304 is formed by the LFRT material that extends around the entire profile and defines an interior surface 305. The thickness of the layer 304 may be similar to the long fiber layer described above with reference to FIG. 11. Contrary to the embodiment of FIG. 11, however, the profile 316 does not contain a CFRT layer around the entire periphery of the profile. Instead, the CFRT material is provided as a discrete vertical layer 306 a and horizontal layer 306 b within the interior of the profile 316. A capping layer 307 is likewise provided that extends around the periphery of the inner layer 304 and defines an external surface 308 of the profile 316.
  • [0093]
    Still another embodiment of a hollow profile is shown in FIG. 16. In this embodiment, the profile 416 has a generally L-shaped cross-section. An inner layer 406 of the L-shaped profile 416 may include the CFRT material and an outer layer 404 may include the LFRT material. Discrete layers 409 of CFRT material may also be employed. Further, a capping layer 407 may extend around the entire periphery of the profile 416 and define an external surface 408 thereof.
  • [0094]
    The embodiments described above contain the LFRT and CFRT materials in separate layers so that selective reinforcement may be provided to the profile. However, this is by no means required. In fact, in certain embodiments of the present invention, the long fiber material is integrated into the continuous fiber ribbon so that the materials are not provided as separate layers. This may be accomplished, for instance, by incorporating the long fiber material into the continuous ribbon during impregnation.
  • [0095]
    Referring again to FIGS. 2-3, for example, long fiber pellets (not shown) containing a plurality of long fibers randomly distributed within a second thermoplastic matrix may be supplied to the hopper 126 and combined with the first thermoplastic matrix 127. In this manner, the long fiber pellets are melt-blended with the first thermoplastic matrix used to impregnate the continuous fiber strands and create an extrudate 152 that contains continuous fibers, long fibers, and two different thermoplastic matrices, which may include the same or different polymers. In the alternative, the long fibers may be added directly to the hopper 126 without being pre-embedded with a thermoplastic matrix. In such embodiments, the first thermoplastic matrix will encapsulate both the continuous and long fibers. Regardless of the technique employed, however, the long fiber material may be distributed in a substantially homogeneous manner throughout the profile. One example of such a profile is shown in FIG. 17 as element 516. In this embodiment, the profile 516 is generally rectangular in shape and contains a continuous fiber ribbon 514 within which is distributed a plurality of long fibers 518. A capping layer 519 also extends around the perimeter of the ribbon 514 and defines an external surface of the profile 516. It should also be understood that such “hybrid” ribbons, which contain both continuous and long fibers, may also be combined with one or more additional ribbons as described above. These additional ribbons may contain continuous fibers, long fibers, or combinations thereof, and may be pre-manufactured or made in line.
  • [0096]
    As will be appreciated, the particular profile embodiments described above are merely exemplary of the numerous designs that are made possible by the present invention. Among the various possible profile designs, it should be understood that additional layers of continuous and/or long fiber material may be employed in addition to those described above. Further, the embodiments described above are generally considered “lineal” profiles to the extent that they possess a cross-sectional shape that is substantially the same along the entire length of the profile. It should be understood, however, that profiles may also be formed in the present invention that have a varying cross-sectional shape, such as curved, twisted, etc.
  • [0097]
    The present disclosure may be better understood with reference to the following example.
  • Example
  • [0098]
    Continuous fiber ribbons were initially formed using an extrusion system as substantially described above and shown in FIGS. 2-3. Glass fiber rovings (E-glass, 2200 tex) were employed for the continuous fibers with each individual ribbon containing three (3) fiber rovings. The thermoplastic polymer used to impregnate the fibers was acrylonitrile butadiene styrene (ABS), which has a melting point of about 105° C. Each ribbon contained 60 wt. % glass fibers and 40 wt. % ABS. The resulting ribbons had a thickness of between 0.2 to 0.4 millimeters and a void fraction of less than 1%. Once formed, the ribbons were then fed to an extrusion/pultrusion line operating at a speed of 5 feet per minute. Prior to consolidation, the ribbons were heated within an infrared oven (power setting of 160). The heated ribbons were then supplied to a consolidation die having a U-shaped channel that received the ribbons and consolidated them together while forming the initial shape of the profile. Within the die, the ribbons remained at a temperature of about 121° C., just above the melting point of the ABS matrix. Upon consolidation, the resulting laminate was then briefly cooled with ambient air. The laminate was then passed through the pultrusion die as shown in FIG. 1. Long fiber pellets were applied to the interior section of the U-shaped profile at 246° C.
  • [0099]
    The resulting part was then supplied to a 1-inch land section to impart the final “U shape” and cooled using an oil cooled sizing unit set at a temperature of about 26° C. Air cooling was then employed to complete the cooling process. The profile had a thickness of approximately 3.2 millimeters and a width of approximately 40 millimeters. While this particular part formed had a U-shape, it should be understood that a substantially rectangular hollow profile may simply be formed from two different U-shaped laminates in the manner described above and shown herein.
  • [0100]
    Ten (10) different U-shaped profile samples were formed as described above with different amounts of continuous fibers and long fibers. The amount of long fibers was varied by using different percentages of long fibers in the pellets, ranging from 0 wt. % to 40.%, and the amount of continuous fibers was varied by using different numbers of ribbons, ranging from 2 to 7. The manner in which each of the samples was formed is reflected below in Table 1.
  • [0000]
    TABLE 1
    Wt Ratio of
    Long Fibers Number of Continuous Fiber
    in Pellets Continuous Material to Long
    Sample (wt. %) Fiber Ribbons Fiber Material
    1 0 7
    2 20 2 1.21
    3 20 3 1.99
    4 20 4 3.20
    5 30 2 0.72
    6 30 3 1.54
    7 30 4 2.34
    8 40 2 0.57
    9 40 3 0.95
    10 40 4 1.52
  • [0101]
    To determine the strength properties of the U-shaped profile, three-point flexural testing was performed in accordance with ASTM D790-10, Procedure A. One transverse edge of the profile was supported with a fixture, and the load from the Instron meter was applied to the free edge of the U profile. The following equation was used to calculate the maximum stress load on the part: Maximum stress load=(6*Pmax*L)/w*t2 where Pmax=maximum load, L=length of lever arm, w=sample width, t=sample thickness. The strength properties of the samples are set forth below in Table 2.
  • [0000]
    TABLE 2
    Ratio of
    Maximum Flexural
    Flexural Flexural Modulus
    Strength Modulus to Flexural
    Sample (MPa) (GPa) Strength
    1 11.73 26.6 2268
    2 35.39 6.2 175
    3 32.36 8.7 269
    4 32.76 13.7 418
    5 30.94 7.87 254
    6 27.17 13.55 499
    7 26.57 14.87 560
    8 27.93 11.82 423
    9 26.57 13.75 518
    10 29.66 14.75 497
  • [0102]
    It should be understood that the strength properties of the U-shaped parts referenced above would be substantially equivalent to a substantially rectangular hollow profile part due to the fact that such a profile is a combination of two U-shaped parts, and that the strength properties would be determined by cross-sectioning the hollow profile into a U-shaped part for testing purposes.
  • [0103]
    These and other modifications and variations of the present invention may be practiced by those of ordinary skill in the art, without departing from the spirit and scope of the present invention. In addition, it should be understood that aspects of the various embodiments may be interchanged both in whole or in part. Furthermore, those of ordinary skill in the art will appreciate that the foregoing description is by way of example only, and is not intended to limit the invention so further described in such appended claims.

Claims (22)

  1. 1-31. (canceled)
  2. 32. A method for forming a hollow profile that extends in a longitudinal direction, the method comprising:
    impregnating a plurality of continuous fibers with a thermoplastic matrix within an extrusion device;
    consolidating the impregnated fibers to form a first ribbon in which the continuous fibers are oriented in the longitudinal direction;
    pultruding the first ribbon and a plurality of long fibers through a die to form the hollow profile.
  3. 33. The method of claim 32, wherein the continuous fibers, long fibers, or both, include glass fibers, carbon fibers, or a combination of glass and carbon fibers.
  4. 34. The method of claim 32, wherein the thermoplastic polymer matrix includes a polyolefin, polyether ketone, polyetherimide, polyarylene ketone, liquid crystal polymer, polyarylene sulfide, fluoropolymer, polyacetal, polyurethane, polycarbonate, styrenic polymer, polyester, polyamide, or a combination thereof.
  5. 35. The method of claim 32, wherein the first ribbon has a void fraction of about 2% or less.
  6. 36. The method of claim 32, wherein a manifold assembly supplies the thermoplastic matrix to the extrusion device, the manifold assembly comprising branched runners through which the thermoplastic matrix flows.
  7. 37. The method of claim 32, wherein the profile exhibits a flexural modulus and maximum flexural strength in the transverse direction, wherein the ratio of the flexural modulus to the maximum flexural strength is from about 50 to about 2200.
  8. 38. The method of claim 32, wherein the profile exhibits a flexural modulus of about 2 Gigapascals or more.
  9. 39. The method of claim 32, wherein the profile exhibits a maximum flexural strength of about 12 Megapascals or more.
  10. 40. The method of claim 32, wherein the long fibers are embedded within a second thermoplastic matrix.
  11. 41. The method of claim 40, wherein the second thermoplastic polymer matrix includes a polyolefin, polyether ketone, polyetherimide, polyarylene ketone, liquid crystal polymer, polyarylene sulfide, fluoropolymer, polyacetal, polyurethane, polycarbonate, styrenic polymer, polyester, polyamide, or a combination thereof.
  12. 42. The method of claim 32, wherein about 10% or more of the long fibers are oriented at an angle relative to the longitudinal direction.
  13. 43. The method of claim 32, wherein the profile has a generally rectangular shape.
  14. 44. The method of claim 32, wherein the long fibers are included within a first layer of the profile and the first ribbon is included within a second layer of the profile, the first layer being positioned adjacent to the second layer.
  15. 45. The method of claim 44, wherein the first layer forms an inner layer of the hollow profile.
  16. 46. The method of claim 45, wherein the second layer extends substantially around the periphery of the first layer.
  17. 47. The method of claim 45, wherein the second layer is located in one or more discrete regions adjacent to the first layer.
  18. 48. The method of claim 44, wherein the second layer forms an inner layer of the hollow profile.
  19. 49. The method of claim 48, wherein the first layer extends substantially around the periphery of the second layer.
  20. 50. The method of claim 48, wherein the first layer is located in one or more discrete regions adjacent to the second layer.
  21. 51. The method of claim 32, wherein the cross-section shape of the profile is substantially the same along the entire length of the profile.
  22. 52. The method of claim 32, wherein the long fibers are included within the first ribbon.
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Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2013102598A (en) * 2010-06-22 2014-07-27 ТИКОНА ЭлЭлСи Reinforced hollow profiles
EP2697801B8 (en) 2011-04-12 2016-05-11 Ticona LLC Composite core for electrical transmission cables
US9346222B2 (en) 2011-04-12 2016-05-24 Ticona Llc Die and method for impregnating fiber rovings
JP2014516822A (en) * 2011-04-12 2014-07-17 ティコナ・エルエルシー Extrusion for thermoplastic rods and manufacturing reinforced with continuous fibers
EP2697799B1 (en) 2011-04-12 2016-05-25 Ticona LLC Umbilical for use in subsea applications
CA2775445A1 (en) 2011-04-29 2012-10-29 Ticona Llc Die and method for impregnating fiber rovings
CN104053530B (en) 2011-04-29 2016-10-19 提克纳有限责任公司 And a die casting method of the flow path for the diffusion of impregnated fiber roving
US9283708B2 (en) 2011-12-09 2016-03-15 Ticona Llc Impregnation section for impregnating fiber rovings
WO2013086269A1 (en) 2011-12-09 2013-06-13 Ticona Llc Impregnation section of die for impregnating fiber rovings
US9410644B2 (en) 2012-06-15 2016-08-09 Ticona Llc Subsea pipe section with reinforcement layer
DE102012111097A1 (en) * 2012-11-19 2014-05-22 Dbw Holding Gmbh Composite component thereof and methods of making thereof
FR3003195B1 (en) * 2013-03-15 2015-07-31 Faurecia Automotive Composites Method and device for producing a profile of a thermoplastic material reinforced with fibers, comprising a tensioning step of the fibers during their impregnation
FR3003194B1 (en) * 2013-03-15 2015-04-17 Faurecia Automotive Composites Method and device for producing a profile of a thermoplastic material reinforced with fibers, comprising a step of regulating the temperature of the thermoplastic material
US9222269B2 (en) * 2013-12-19 2015-12-29 National Nail Corp. Reinforced composite decking and related method of manufacture
US20170050365A1 (en) * 2014-04-30 2017-02-23 Zephyros, Inc. Extruded reinforcements

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5174844A (en) * 1986-11-26 1992-12-29 Industrial Technology Research Institute Method and means for making pultruded fiber reinforced articles
US5266139A (en) * 1992-10-02 1993-11-30 General Dynamics Corporation, Space Systems Division Continuous processing/in-situ curing of incrementally applied resin matrix composite materials
US5534210A (en) * 1994-01-26 1996-07-09 Polyplastics Co., Ltd. Method of taking out a fiber bundle and method of manufacturing a resin structure reinforced with long fibers
US20070125301A1 (en) * 2005-12-01 2007-06-07 Xixian Zhou System and die for forming a continuous filament reinforced structural plastic profile by pultrusion/coextrusion
US20070243368A1 (en) * 2005-10-11 2007-10-18 Edwards Christopher M Composite article

Family Cites Families (125)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3669158A (en) 1969-03-10 1972-06-13 Technology Uk Continuous carbon fiber tapes
GB1302049A (en) 1969-06-17 1973-01-04
FR2266595B1 (en) 1974-04-05 1976-10-08 Peugeot & Renault
GB2041489A (en) 1978-09-29 1980-09-10 Courtaulds Ltd Composite elongate element
USRE32772E (en) 1979-09-13 1988-10-25 Polymer Composites, Inc. Method of manufacturing a composite reinforcing structure
JPS5738137A (en) 1980-08-21 1982-03-02 Mitsubishi Petrochemical Co Manufacture of composite member
US4549920A (en) 1981-07-28 1985-10-29 Imperial Chemical Industries, Plc Method for impregnating filaments with thermoplastic
EP0102159B1 (en) 1982-07-28 1988-01-27 Imperial Chemical Industries Plc Method of producing fibre-reinforced composition
US4564540A (en) 1982-12-08 1986-01-14 Davies Lawrence W Pultruded fibreglass spacer for sealed window units
GB8400032D0 (en) 1984-01-03 1984-02-08 Omniglass Ltd Pultruded window frame
DE3408224A1 (en) 1984-03-07 1985-09-19 Bayer Ag Langfaserverstaerktes thermoplastic semi-finished
US4874563A (en) 1984-03-15 1989-10-17 Basf Structural Materials Inc. Process for preparing tows from composite fiber blends
US4588538A (en) 1984-03-15 1986-05-13 Celanese Corporation Process for preparing tapes from thermoplastic polymers and carbon fibers
US4681722A (en) 1985-10-07 1987-07-21 Owens-Corning Fiberglas Corporation Method of making a lineal structural member
US4640065A (en) 1985-10-07 1987-02-03 Owens-Corning Fiberglas Corporation Structural member
JPH0620743B2 (en) 1985-12-26 1994-03-23 出光石油化学株式会社 Composite long fiber-reinforced thermoplastic resin Sutanpaburushi - DOO and bumper by molding it - bi - beam
US5128198A (en) 1986-11-07 1992-07-07 Basf Aktiengesellschaft Production of improved preimpregnated material comprising a particulate thermoplastic polymer suitable for use in the formation of a substantially void-free fiber-reinforced composite article
US4792481A (en) 1986-11-28 1988-12-20 Phillips Petroleum Company Reinforced plastic
US4752313A (en) 1986-12-16 1988-06-21 Corning Glass Works Pultrusion process for fiber-reinforced composites
FR2610864B1 (en) 1987-02-18 1989-06-16 Atochem profiles manufacturing method of thermoplastic polymer by pultrusion - equipment - products obtained
US5026410A (en) 1987-03-12 1991-06-25 Owens-Corning Fiberglas Corporation Process for impregnating filament strands
US4752513A (en) 1987-04-09 1988-06-21 Ppg Industries, Inc. Reinforcements for pultruding resin reinforced products and novel pultruded products
GB8709455D0 (en) 1987-04-22 1987-05-28 Strachan R In-line core filled pultruded profiles
EP0308237B1 (en) 1987-09-17 1994-08-10 Tonen Corporation Carbon fibre-reinforced composite resin pultrusion products and method for manufacturing the same
GB8801259D0 (en) 1988-01-20 1988-02-17 Secr Defence Digital modulator
US5098496A (en) 1988-06-30 1992-03-24 Shell Oil Company Method of making postformable fiber reinforced composite articles
US4938823A (en) 1988-10-07 1990-07-03 The Pultrusions Corporation Pultrusion/extrusion method
CA1336483C (en) 1989-01-30 1995-08-01 Hatsuo Ishida Process for preparing composites
US5026447A (en) 1989-02-10 1991-06-25 Phillips Petroleum Company Method for making variable cross section pultruded thermoplastic composite articles
US4992229A (en) 1989-02-14 1991-02-12 Phillips Petroleum Company Thermoplastic re-pultrusion
WO1991000796A1 (en) 1989-07-10 1991-01-24 Ube-Nitto Kasei Co., Ltd. Stampable sheet made of fiber-reinforced thermoplastic resin and molded article thereof
US4984402A (en) 1989-09-29 1991-01-15 Omniglass Ltd. Sash window arrangement
US5091036A (en) 1989-10-05 1992-02-25 Taylor Scott R Apparatus for pultruding thermoplastic structures at below melt temperatures
DE69115891D1 (en) 1990-02-22 1996-02-08 New Millennium Composites Ltd Fiber-reinforced composite materials
JP2983569B2 (en) 1990-03-02 1999-11-29 ポリプラスチックス株式会社 Molded articles made of preparation and the resin of the long-fiber-reinforced thermoplastic polyester resin
DE69128374T2 (en) 1990-03-30 1998-04-02 Kuraray Co A process for producing a fiber reinforced product produced in this manner and Thermoplastkunststoffgiesserzeugnisses
US5095632A (en) 1990-06-15 1992-03-17 Parker Hannifin Corporation Composite structure unidirectionally stable with respect to thermal and moisture expansion
US5198172A (en) 1990-07-23 1993-03-30 Phillips Petroleum Company Method of pultruding utilizing a die with changeable die insects
JPH06503517A (en) 1990-08-16 1994-04-21
US5114516A (en) 1990-10-05 1992-05-19 Aluminum Company Of America Method for pultruding fiber-reinforced, thermoplastic stock
US5888609A (en) * 1990-12-18 1999-03-30 Valtion Teknillinen Tutkimuskeskus Planar porous composite structure and method for its manufacture
US5336526A (en) 1991-04-12 1994-08-09 Phillips Petroleum Company Primary processing of laminated thermoplastic sheets
US5225020A (en) 1991-08-20 1993-07-06 W. R. Grace & Co.-Conn. Pultrusion mandrel with integral, intercooled resin injector and method of using the same
US5552215A (en) 1991-10-09 1996-09-03 United Technologies Corporation Fiber reinforced glass matrix composites with secondary matrix reinforcement
GB9127003D0 (en) 1991-12-19 1992-02-19 Shaw John Ltd Pultruded composites
US5492583A (en) 1992-11-16 1996-02-20 Geotek, Inc. Apparatus and method for in-line coating of pultrusion profiles
US5492743A (en) 1992-12-21 1996-02-20 Xerox Corporation Pultruded member with functional features
US5902755A (en) 1993-05-03 1999-05-11 Tox-Wastech, Inc. High Strength composite materials
US5401154A (en) 1993-05-26 1995-03-28 Continental Structural Plastics, Inc. Apparatus for compounding a fiber reinforced thermoplastic material and forming parts therefrom
JPH07216104A (en) 1994-01-26 1995-08-15 Polyplastics Co Preparation of long filament-reinforced resin structure
EP0691903B1 (en) 1994-01-28 1998-12-30 ISOSPORT VERBUNDBAUTEILE Ges.m.b.H. Process and device for producing glass fibre mat reinforced thermoplastic boards
DE4421184A1 (en) 1994-06-17 1995-12-21 Siemens Ag Cable reinforcing core, of sufficient dia. to carry multiple outer conductors
US5792529A (en) 1994-12-21 1998-08-11 Intek Weatherseal Products, Inc. Reinforced plastic extrusion
US5556496A (en) 1995-01-10 1996-09-17 Sumerak; Joseph E. Pultrusion method for making variable cross-section thermoset articles
GB9501605D0 (en) 1995-01-27 1995-03-15 Kobe Steel Europ Ltd Radiation-curable compositions
US5585155A (en) 1995-06-07 1996-12-17 Andersen Corporation Fiber reinforced thermoplastic structural member
US5783013A (en) 1995-06-07 1998-07-21 Owens-Corning Fiberglas Technology Inc. Method for performing resin injected pultrusion employing multiple resins
US5747075A (en) 1995-06-07 1998-05-05 Owens-Corning Fiberglas Technology Inc. Apparatus for resin ipregnated pultrusion
JP2877052B2 (en) 1995-12-01 1999-03-31 東洋紡績株式会社 Fiber-reinforced thermoplastic resin sheet - DOO
US6045876A (en) 1996-04-10 2000-04-04 Fellers; John F. System and method for impregnating a continuous fiber strand with a polymer melt
US5840370A (en) 1996-05-02 1998-11-24 Owens Corning Fiberglas Technology, Inc. In-line processing of continous glass fibers with thermoset solution epoxy
US5727357A (en) 1996-05-22 1998-03-17 Owens-Corning Fiberglas Technology, Inc. Composite reinforcement
US5882564A (en) 1996-06-24 1999-03-16 Andersen Corporation Resin and wood fiber composite profile extrusion method
US5779961A (en) 1996-07-26 1998-07-14 General Electric Company Method of making a fiber reinforced thermoplastic extrusion
GB9615995D0 (en) 1996-07-30 1996-09-11 Kobe Steel Europ Ltd Fibre reinforced compositions and methods for their production
US6037056A (en) 1997-01-08 2000-03-14 Owens Corning Fiberglas Technology, Inc. Transversely and axially reinforced pultrusion product
US6090319A (en) 1997-01-14 2000-07-18 Ticona Celstran, Inc. Coated, long fiber reinforcing composite structure and process of preparation thereof
US6122877A (en) 1997-05-30 2000-09-26 Andersen Corporation Fiber-polymeric composite siding unit and method of manufacture
US6387179B1 (en) 1997-06-24 2002-05-14 Hydril Company Method and device for impregnating fiber bundles with resin
US5911932A (en) 1997-07-09 1999-06-15 R. Charles Balmer Method of prepregging with resin
US6821613B1 (en) 1998-04-15 2004-11-23 Rcc Regional Compact Car Ag Structural component consisting of fiber-reinforced thermoplastic plastic
US20020061374A1 (en) * 1999-01-29 2002-05-23 O'brien Frank Composite tubular member having impact resistant member
US6872273B2 (en) 1999-06-21 2005-03-29 Pella Corporation Method of making a pultruded part with a reinforcing mat
CA2377744C (en) 1999-06-21 2006-08-08 Pella Corporation Pultruded part and method of preparing a reinforcement mat for the part
US6881288B2 (en) 1999-06-21 2005-04-19 Pella Corporation Method of making a reinforcing mat for a pultruded part
US20020123288A1 (en) 1999-06-21 2002-09-05 Pella Corporation Pultruded part with reinforcing mat
US6346325B1 (en) 1999-07-01 2002-02-12 The Dow Chemical Company Fiber-reinforced composite encased in a thermoplastic and method of making same
DE19930920A1 (en) 1999-07-06 2001-01-11 Fact Future Advanced Composite the same long-fiber reinforced thermoplastic material and methods for preparing
US6260251B1 (en) 1999-08-31 2001-07-17 Andersen Corporation Unitary profile for window construction
EP1224111B1 (en) 1999-10-20 2004-01-02 RCC Regional Compact Car AG Fiber-reinforced thermoplastic vehicle cell
WO2001051544A3 (en) 2000-01-13 2002-03-07 Dow Chemical Co Process for in-line forming of pultruded composites
EP1250504A1 (en) 2000-01-13 2002-10-23 Dow Global Technologies Inc Composites of reinforcing fibers and thermoplastic resins as external structural supports
DE10015984A1 (en) 2000-03-31 2001-10-18 Ticona Gmbh Long fiber-reinforced polyolefin structure used for colored parts comprises polyolefin(s), polyamide(s), modified polyolefin(s), reinforcing fiber(s) and sulfur-containing additive(s)
FR2807966B1 (en) 2000-04-25 2003-01-17 Vetrotex France Sa Method and device for manufacturing a composite profile shape of thermoplastic organic material reinforced by reinforcing fibers
EP1160072A3 (en) 2000-05-30 2002-11-06 Nippon Steel Composite Co., Ltd. Continuous reinforcing fiber sheet and manufacturing method thereof
US6811861B2 (en) 2000-11-28 2004-11-02 Wisconsin Alumni Research Foundation Structural reinforcement using composite strips
US6955735B2 (en) 2001-01-31 2005-10-18 Kusek Walter W Pultrusion with plastisol
US6763869B2 (en) 2001-03-07 2004-07-20 Chisso Corporation Device for producing thermoplastic resin continuous length sections reinforced with long fibers
US7105071B2 (en) 2001-04-06 2006-09-12 Ebert Composites Corporation Method of inserting z-axis reinforcing fibers into a composite laminate
US20030003265A1 (en) 2001-06-14 2003-01-02 Davies Laurence W. Pultruded part reinforced by longitudinal and transverse fibers and a method of manufacturing thereof
US7514135B2 (en) 2001-06-14 2009-04-07 Omniglass Ltd. Pultruded part reinforced by longitudinal and transverse fibers and a method of manufacturing thereof
US20030096096A1 (en) 2001-11-19 2003-05-22 Jo Byeong H. Plastic rail system reinforced with fiberglass thermoplastic composites
CN1385296A (en) * 2002-06-07 2002-12-18 柳惠平 Technological method for pultrusion of glass fibre reinforced plastics pipe and die thereof
DE50308436D1 (en) 2002-09-15 2007-11-29 Weber Technology Ag Structural component, Process and apparatus for manufacturing structural components from fiber-reinforced thermoplastic material
DE50306774D1 (en) 2002-09-15 2007-04-19 Weber Technology Ag Structural component of fiber reinforced thermoplastic material
DE60320134T3 (en) * 2002-11-28 2015-12-24 Mitsubishi Rayon Co., Ltd. Manufacturing processes for fiber-reinforced composite material
WO2004080698A1 (en) 2003-03-06 2004-09-23 Ticona Celstran, Inc. Method of making long fiber-reinforced thermoplastic composites utilizing hybrid or commingled yarn
US7249943B2 (en) 2003-08-01 2007-07-31 Alliant Techsystems Inc. Apparatus for forming composite stiffeners and reinforcing structures
CN100411848C (en) * 2004-01-12 2008-08-20 天津市金锚科技发展有限公司 Tectorial perform device and pultruder having the device
WO2006044315A3 (en) 2004-10-13 2007-02-01 Christopher M Edwards Composite article
US7413623B2 (en) 2005-02-04 2008-08-19 Rse Industries, Inc. Apparatus for resin-impregnation of fibers for filament winding
US20090023870A1 (en) 2006-02-07 2009-01-22 Resin Systems, Inc Method of Pultrusion Employing Multiple Resins
US20060280938A1 (en) 2005-06-10 2006-12-14 Atkinson Paul M Thermoplastic long fiber composites, methods of manufacture thereof and articles derived thererom
US8212194B2 (en) 2006-06-27 2012-07-03 Hexcel Corporation Aerospace articles made from quasi-isotropic chopped prepreg
US9545760B2 (en) 2005-08-18 2017-01-17 Teijin Limited Isotropic fiber-reinforced thermoplastic resin sheet, and process for production and molded plate thereof
US7601282B2 (en) 2005-10-24 2009-10-13 Johns Manville Processes for forming a fiber-reinforced product
US8597016B2 (en) 2005-11-23 2013-12-03 Milgard Manufacturing Incorporated System for producing pultruded components
US8101107B2 (en) 2005-11-23 2012-01-24 Milgard Manufacturing Incorporated Method for producing pultruded components
US7901762B2 (en) 2005-11-23 2011-03-08 Milgard Manufacturing Incorporated Pultruded component
US8852475B2 (en) 2005-12-01 2014-10-07 Saint-Gobain Performance Plastics Corporation Method of making continuous filament reinforced structural plastic profiles using pultrusion/coextrusion
US7597771B2 (en) 2006-02-07 2009-10-06 Comfort Line Ltd. Pultrusion method and related article
CA2540747A1 (en) 2006-03-22 2007-09-22 Resin Systems Inc. Pultrusion apparatus and method
US20080300355A1 (en) 2006-08-25 2008-12-04 Ticona, Llc Process For Forming Improved Fiber Reinforced Composites and Composites Therefrom
US20080081862A1 (en) * 2006-10-03 2008-04-03 Arnold Lustiger Fiber reinforced polystyrene composites
US20090011210A1 (en) 2007-02-15 2009-01-08 Xiao Gao Lightweight glass fiber reinforced thermoplastic material
CN201046603Y (en) * 2007-03-23 2008-04-16 飞 董 Drawing-squeezing fiber reinforcement pipes forming machine
DE102008013467A1 (en) 2007-03-23 2008-11-13 Thomas Gmbh + Co. Technik + Innovation Kg Method and apparatus for the production of a plastic profile
GB0707158D0 (en) 2007-04-13 2007-05-23 3M Innovative Properties Co Sign post comprisising composite material
DE102007018052A1 (en) 2007-04-17 2008-10-23 Airbus Deutschland Gmbh Pultrusion process for producing an endless profile
WO2009059012A3 (en) 2007-10-30 2009-07-23 Kermit D Paul Improved fiber reinforced plastic composites and method and apparatus for making
CN102947079A (en) * 2010-06-11 2013-02-27 提克纳有限责任公司 Structural member formed from a solid lineal profile
RU2013102598A (en) * 2010-06-22 2014-07-27 ТИКОНА ЭлЭлСи Reinforced hollow profiles
EP2697799B1 (en) * 2011-04-12 2016-05-25 Ticona LLC Umbilical for use in subsea applications
EP2697801B8 (en) * 2011-04-12 2016-05-11 Ticona LLC Composite core for electrical transmission cables
JP2014516822A (en) * 2011-04-12 2014-07-17 ティコナ・エルエルシー Extrusion for thermoplastic rods and manufacturing reinforced with continuous fibers

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5174844A (en) * 1986-11-26 1992-12-29 Industrial Technology Research Institute Method and means for making pultruded fiber reinforced articles
US5266139A (en) * 1992-10-02 1993-11-30 General Dynamics Corporation, Space Systems Division Continuous processing/in-situ curing of incrementally applied resin matrix composite materials
US5534210A (en) * 1994-01-26 1996-07-09 Polyplastics Co., Ltd. Method of taking out a fiber bundle and method of manufacturing a resin structure reinforced with long fibers
US20070243368A1 (en) * 2005-10-11 2007-10-18 Edwards Christopher M Composite article
US20070125301A1 (en) * 2005-12-01 2007-06-07 Xixian Zhou System and die for forming a continuous filament reinforced structural plastic profile by pultrusion/coextrusion

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