US20170241044A1 - Yarn for reinforcing composite materials - Google Patents

Yarn for reinforcing composite materials Download PDF

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Publication number
US20170241044A1
US20170241044A1 US15/441,673 US201715441673A US2017241044A1 US 20170241044 A1 US20170241044 A1 US 20170241044A1 US 201715441673 A US201715441673 A US 201715441673A US 2017241044 A1 US2017241044 A1 US 2017241044A1
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Prior art keywords
yarn
treating
carbon nanotubes
manufacture
resinous matrix
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US15/441,673
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David W. Gailus
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Nanocomp Technologies Inc
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Nanocomp Technologies Inc
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Priority to US15/441,673 priority Critical patent/US20170241044A1/en
Publication of US20170241044A1 publication Critical patent/US20170241044A1/en
Priority to US17/331,305 priority patent/US20210277594A1/en
Abandoned legal-status Critical Current

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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/70—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment combined with mechanical treatment
    • D—TEXTILES; PAPER
    • D02—YARNS; MECHANICAL FINISHING OF YARNS OR ROPES; WARPING OR BEAMING
    • D02G—CRIMPING OR CURLING FIBRES, FILAMENTS, THREADS, OR YARNS; YARNS OR THREADS
    • D02G3/00—Yarns or threads, e.g. fancy yarns; Processes or apparatus for the production thereof, not otherwise provided for
    • D02G3/02—Yarns or threads characterised by the material or by the materials from which they are made
    • D02G3/16—Yarns or threads made from mineral substances
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/08—Interconnection of layers by mechanical means
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/16—Preparation
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/53—Polyethers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/55—Epoxy resins
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/564—Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/59—Polyamides; Polyimides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/61—Polyamines polyimines
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/005—Applying monomolecular films on textile products like fibres, threads or fabrics
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B2038/0052—Other operations not otherwise provided for
    • B32B2038/008—Sewing, stitching
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/07—Parts immersed or impregnated in a matrix
    • B32B2305/076—Prepregs
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/514—Oriented
    • B32B2307/518—Oriented bi-axially
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/546—Flexural strength; Flexion stiffness
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/40—Fibres of carbon
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2101/00—Inorganic fibres
    • D10B2101/10—Inorganic fibres based on non-oxides other than metals
    • D10B2101/12—Carbon; Pitch
    • D10B2101/122—Nanocarbons
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2505/00—Industrial
    • D10B2505/02—Reinforcing materials; Prepregs

Definitions

  • the invention relates to composite materials, and in particular, to suppressing delamination of such materials.
  • Composite materials are typically made of layers that have been joined together. As a result, a composite material is inherently anisotropic. Its response to force is a function of the direction of the force vector.
  • the composite material is remarkably strong. However, the same force, when acting in a disfavored direction, can have catastrophic results. This is because the composite material has a tendency to delaminate.
  • the invention features a yarn made of carbon nanotubes.
  • the yarn has been treated to promote interaction with a resinous matrix, such as that which one might find in the interstitial spaces of a composite material.
  • the yarn has also been treated to enable a stitching machine to use the yarn to stitch into a composite material.
  • the yarn includes pre-treatment resin with which it has been infiltrated.
  • This pre-treatment resin is one that has been selected to fuse with a resinous matrix of a composite material.
  • the yarn includes epoxy, such as B-stage epoxy, with which it has been treated.
  • the yarn includes thermoplastic with which it has been treated.
  • thermoplastic examples include PEEK, PEI, urethane-based plastic, and thermoplastic polyimide.
  • the yarn includes thermoset material with which it has been treated.
  • suitable thermoset materials include epoxy, and polyimide.
  • the yarn has been treated to promote absorption of resinous material.
  • the yarn has been treated to promote swelling upon exposure to resinous material.
  • Further embodiments include a plurality of layers having interstitial spaces filled with the resinous matrix.
  • the yarn passes through the layers.
  • Embodiments further include those in which the carbon nanotubes are single-walled nanotubes and those in which they are multi-walled nanotubes.
  • the carbon nanotubes are manufactured at high temperatures, for example, above 1000 C, and preferably at 1100 C. Such carbon nanotubes tend to be longer and thinner than those formed at lower temperature, and are thus more amenable to being wound into yarn.
  • Another aspect of the invention is a method that includes forming carbon nanotubes, spinning the carbon nanotubes into a yarn, and treating the yarn to promote interaction with a resinous matrix.
  • Other practices include infiltrating the yarn with a pre-treatment resin selected to fuse with a resinous matrix of a composite material.
  • a pre-treatment resin selected to fuse with a resinous matrix of a composite material. Examples include epoxy and B-stage epoxy.
  • thermoplastic examples of which include PEEK, PEI, urethane-based plastic, and thermoplastic polyimide.
  • thermoset material such as epoxy and polyimide.
  • Further practices include treating the yarn to promote absorption of resinous material and treating the yarn to promote swelling upon exposure to resinous material.
  • forming the nanotubes includes forming single-walled nanotubes. However, in other practices, forming nanotubes includes multi-walled nanotubes.
  • Yet other practices feature the use of high temperatures during the formation of carbon nanotubes. Carbon nanotubes formed at high temperatures tend to be longer and thinner than those formed at lower temperature, and are thus more amenable to being wound into yarn. Among these practices are those in which the nanotubes are formed at temperatures above 1000 C, and preferably at 1100 C.
  • FIG. 1 shows a composite material reinforced with a yarn
  • FIG. 2 shows steps in the manufacture of the composite material shown in FIG. 1 .
  • FIG. 1 shows a reinforced composite material 10 having a plurality of layers 12 oriented parallel to a material plane.
  • the layers have been stitched together by a yarn 14 that passes through all the layers 12 .
  • the yarn 14 passes through the layers in a direction normal to the material plane. However, this need not be the case. In other embodiments, the yarn 14 passes through the layers at an angle. In either case, the presence of this yarn 14 tends to suppress the possibility of delamination in response to an impulsive force acting in this normal direction.
  • a suitable yarn 14 is one made of carbon nanotubes that are long enough to spin into a fiber that can then be used to make the yarn 14 .
  • these nanotubes have one wall. In others, they have two or more coaxial walls.
  • the nanotubes to be spun into a fiber are formed at higher temperatures, typically above 1000 C, and preferably at or around 1100 C. This results in formation of nanotubes that are longer and thinner than those formed at lower temperatures and that are therefore more suitable for spinning into a fiber.
  • the yarn 14 is made of four strands of carbon nanotube fibers that have been twisted together to form helices having a particular pitch.
  • the helical pitch is such that the helical angle is around 15 degrees.
  • the resulting yarn 14 is then treated to promote inter-tubal interactions and to increase load transfer between nanotubes, thereby increasing bulk tensile strength.
  • One such treatment is to densify the nanotubes.
  • Another treatment is to cross-link the nanotubes.
  • Carbon nanotubes are particularly useful because they are inherently flexible. Therefore a yarn made from such carbon nanotubes will not be stiff, but will in fact have considerable flexibility. Such a yarn can therefore easily be passed through a conventional stitching machine.
  • a resinous matrix 16 fills interstitial spaces between the various structural elements of the material. As a result, it is particularly useful to pre-treat the yarn 14 to promote bonding between the yarn 14 and this resinous matrix 16 . This can be carried out in several ways.
  • One way to promote bonding between the yarn 14 and the resinous matrix 16 is to infiltrate the yarn 14 itself with B-stage epoxy.
  • Another way to promote bonding between the yarn 14 and the resinous matrix 16 is to infiltrate the yarn 14 with a pre-treatment resin that fuses with the resinous matrix 16 .
  • the pre-treatment resin penetrates all the way through the fibers so that more than just the surface of the yarn interacts with the resinous matrix 16 .
  • the resulting yarn is preferably greater than 50% carbon nanotube by volume with the balance being taken up by the pre-treatment resin.
  • Suitable pre-treatment resins for this application are thermoset materials, such as epoxy or a polyimide, both of which require curing as part of the manufacturing process.
  • Other pre-treatment resins include thermoplastics, such as PEEK, PEI, urethanes, and thermoplastic polyimides.
  • a third way to promote such bonding avoids adding material to the yarn 14 . Instead, this method involves conditioning the yarn 14 to promote absorption of resin from the resinous matrix 16 during reflow and curing. Such absorption will promote swelling of the yarn 14 , thus creating a mechanical interlock between the composite material 10 and the yarn 14 .
  • the spacing between nanotubes is very small. This promotes capillary action. In particular, for low surface-tension liquid, the resulting capillary pumping pressure can be quite high. As a result, when passed through an environment such as the resinous matrix 16 , the yarn 14 can wick prodigious quantities of liquid from the surrounding resin, thus causing the yarn 14 to swell. The now swollen yarn 14 then forms mechanical interlocks with the resinous matrix 16 all along its length. This promotes resistance to delamination.
  • the stitching process can proceed smoothly, without being hampered by the need to handle swollen yarn 14 . It is only after the yarn 14 is safely in place within the composite material 10 that it begins to transition into a state that promotes mechanical interlocking with the surrounding resinous matrix 16 .
  • the ability to mechanically interlock with its surroundings is not the only advantage of the swollen yarn 14 .
  • Such a yarn 14 also develops an advantageous stress-strain curve.
  • the yarn's deformation encompasses a plastic range and an elastic range. Having a plastic range is disadvantageous because a yarn 14 that has been deformed to such an extent does not recover its original shape.
  • the yarn 14 has essentially no plastic state. Its deformation is primarily elastic. Moreover, the elastic response becomes far less non-linear than it was prior to becoming swollen.
  • the yarn 14 will ultimately spend most of its time bonded to the resinous matrix 16 of the composite material 10 , it still has to be stitched into place. This is generally carried out with a stitching machine. As a result, it is useful for the yarn 14 to have properties that will enable it to interact smoothly with a typical stitching machine.
  • One way to do this is to use a sizing agent on the yarn 14 .
  • sizing agents include a friction-reducing film, which can be solid or liquid, and a coating of spalling, such as from graphite. Sizing agents preferably have the property that although they ease passage of the yarn 14 through the stitching equipment, they have little or no effect on the interaction between the yarn 14 and the resinous matrix 16 of the composite material 10 .
  • FIG. 2 shows a procedure for manufacturing the reinforced composite material 10 shown in FIG. 1 .
  • the procedure begins with forming carbon nanotube fibers with lengths long enough to spin the fibers into yarn 14 (step 18 ). This can be carried out by forming them at elevated temperatures, such as temperatures above 1000 C, and in particular, at or substantially around 1100 C.
  • the next step is to then spin the yarn 14 (step 20 ).
  • step 20 In principle, one could now proceed directly to stitching the yarn 14 through the composite material (step 32 ). However, to promote strength, it is useful to promote interaction between the yarn 14 and the resinous matrix 16 (step 22 ). This can be carried out in one of three ways: by infiltrating the yarn 14 with epoxy (step 24 ), by infiltrating it with thermoplastic (step 26 ), or by conditioning the yarn 14 for absorption of the resin (step 28 ).
  • step 30 it is useful to also pre-treat the yarn 14 so that a commercial stitching machine can easily stitch it into the composite material. This involves application of a sizing agent. Finally, the yarn 14 is ready to actually be stitched through the composite material 10 (step 32 ).

Abstract

A yarn for reinforcing composite material includes carbon nanotubes. The yarn has also been treated to promote interaction with a resinous matrix.

Description

    RELATED APPLICATIONS
  • This application claims the benefit of the Feb. 24, 2016 priority date of U.S. Provisional Application No. 62/299,143, the contents of which are herein incorporated by reference.
    • FIELD OF INVENTION
  • The invention relates to composite materials, and in particular, to suppressing delamination of such materials.
    • BACKGROUND
  • Composite materials are typically made of layers that have been joined together. As a result, a composite material is inherently anisotropic. Its response to force is a function of the direction of the force vector.
  • For forces that come from certain favored directions, the composite material is remarkably strong. However, the same force, when acting in a disfavored direction, can have catastrophic results. This is because the composite material has a tendency to delaminate.
  • To address these undesirable characteristics, it is useful to reinforce the material in some way.
    • SUMMARY
  • In one aspect, the invention features a yarn made of carbon nanotubes. The yarn has been treated to promote interaction with a resinous matrix, such as that which one might find in the interstitial spaces of a composite material.
  • In some embodiments, the yarn has also been treated to enable a stitching machine to use the yarn to stitch into a composite material. This could be carried out by treating the yarn with sizing, with spalling, or with graphite, for example with spalling that includes graphite. It can also be carried out by treating the yarn with friction-reducing film, either in liquid or solid form.
  • In some embodiments, the yarn includes pre-treatment resin with which it has been infiltrated. This pre-treatment resin is one that has been selected to fuse with a resinous matrix of a composite material.
  • In some embodiments, the yarn includes epoxy, such as B-stage epoxy, with which it has been treated.
  • In other embodiments, the yarn includes thermoplastic with which it has been treated. Examples of such thermoplastic include PEEK, PEI, urethane-based plastic, and thermoplastic polyimide.
  • In other embodiments, the yarn includes thermoset material with which it has been treated. Examples of suitable thermoset materials include epoxy, and polyimide.
  • In other embodiments, the yarn has been treated to promote absorption of resinous material.
  • In yet other embodiments, the yarn has been treated to promote swelling upon exposure to resinous material.
  • Further embodiments include a plurality of layers having interstitial spaces filled with the resinous matrix. In these embodiments, the yarn passes through the layers. Among these are embodiments in which, as a result of having absorbed liquid from the resinous matrix, the yarn has become swollen, and those in which the yarn has formed mechanical interlocks with the resinous matrix.
  • Embodiments further include those in which the carbon nanotubes are single-walled nanotubes and those in which they are multi-walled nanotubes.
  • In some embodiments, the carbon nanotubes are manufactured at high temperatures, for example, above 1000 C, and preferably at 1100 C. Such carbon nanotubes tend to be longer and thinner than those formed at lower temperature, and are thus more amenable to being wound into yarn.
  • Another aspect of the invention is a method that includes forming carbon nanotubes, spinning the carbon nanotubes into a yarn, and treating the yarn to promote interaction with a resinous matrix.
  • Among the various practices of this method are those that include treating the yarn to enable a stitching machine to use the yarn to stitch into a composite material. These can include treating the yarn with sizing, with spalling, and with graphite. Also among these practices are those that include treating the yarn with friction-reducing film, whether in solid or liquid form.
  • Other practices include infiltrating the yarn with a pre-treatment resin selected to fuse with a resinous matrix of a composite material. Examples include epoxy and B-stage epoxy.
  • Yet other practices of the invention include treating the yarn with thermoplastic, examples of which include PEEK, PEI, urethane-based plastic, and thermoplastic polyimide.
  • Additional practices include treating the yarn with thermoset material, such as epoxy and polyimide.
  • Further practices include treating the yarn to promote absorption of resinous material and treating the yarn to promote swelling upon exposure to resinous material.
  • In some practices, forming the nanotubes includes forming single-walled nanotubes. However, in other practices, forming nanotubes includes multi-walled nanotubes.
  • Yet other practices feature the use of high temperatures during the formation of carbon nanotubes. Carbon nanotubes formed at high temperatures tend to be longer and thinner than those formed at lower temperature, and are thus more amenable to being wound into yarn. Among these practices are those in which the nanotubes are formed at temperatures above 1000 C, and preferably at 1100 C.
  • These and other features and advantages of the invention will be apparent from the following detailed description and the accompanying figures, in which:
    • BRIEF DESCRIPTION OF THE DRAWINGS
  • FIG. 1 shows a composite material reinforced with a yarn; and
  • FIG. 2 shows steps in the manufacture of the composite material shown in FIG. 1.
    •  DETAILED DESCRIPTION
  • FIG. 1 shows a reinforced composite material 10 having a plurality of layers 12 oriented parallel to a material plane. The layers have been stitched together by a yarn 14 that passes through all the layers 12. In the particular embodiment shown, the yarn 14 passes through the layers in a direction normal to the material plane. However, this need not be the case. In other embodiments, the yarn 14 passes through the layers at an angle. In either case, the presence of this yarn 14 tends to suppress the possibility of delamination in response to an impulsive force acting in this normal direction.
  • A suitable yarn 14 is one made of carbon nanotubes that are long enough to spin into a fiber that can then be used to make the yarn 14. In some cases, these nanotubes have one wall. In others, they have two or more coaxial walls. Unlike conventional nanotubes, which are formed at lower temperatures of 600-700 C, the nanotubes to be spun into a fiber are formed at higher temperatures, typically above 1000 C, and preferably at or around 1100 C. This results in formation of nanotubes that are longer and thinner than those formed at lower temperatures and that are therefore more suitable for spinning into a fiber.
  • In some embodiments, the yarn 14 is made of four strands of carbon nanotube fibers that have been twisted together to form helices having a particular pitch. Preferably, the helical pitch is such that the helical angle is around 15 degrees.
  • The resulting yarn 14 is then treated to promote inter-tubal interactions and to increase load transfer between nanotubes, thereby increasing bulk tensile strength. One such treatment is to densify the nanotubes. Another treatment is to cross-link the nanotubes.
  • Carbon nanotubes are particularly useful because they are inherently flexible. Therefore a yarn made from such carbon nanotubes will not be stiff, but will in fact have considerable flexibility. Such a yarn can therefore easily be passed through a conventional stitching machine.
  • In many composite materials 10, a resinous matrix 16 fills interstitial spaces between the various structural elements of the material. As a result, it is particularly useful to pre-treat the yarn 14 to promote bonding between the yarn 14 and this resinous matrix 16. This can be carried out in several ways.
  • One way to promote bonding between the yarn 14 and the resinous matrix 16 is to infiltrate the yarn 14 itself with B-stage epoxy.
  • Another way to promote bonding between the yarn 14 and the resinous matrix 16 is to infiltrate the yarn 14 with a pre-treatment resin that fuses with the resinous matrix 16. Preferably, the pre-treatment resin penetrates all the way through the fibers so that more than just the surface of the yarn interacts with the resinous matrix 16. The resulting yarn is preferably greater than 50% carbon nanotube by volume with the balance being taken up by the pre-treatment resin. Suitable pre-treatment resins for this application are thermoset materials, such as epoxy or a polyimide, both of which require curing as part of the manufacturing process. Other pre-treatment resins include thermoplastics, such as PEEK, PEI, urethanes, and thermoplastic polyimides.
  • A third way to promote such bonding avoids adding material to the yarn 14. Instead, this method involves conditioning the yarn 14 to promote absorption of resin from the resinous matrix 16 during reflow and curing. Such absorption will promote swelling of the yarn 14, thus creating a mechanical interlock between the composite material 10 and the yarn 14.
  • In a yarn 14 spun from carbon nanotubes, the spacing between nanotubes is very small. This promotes capillary action. In particular, for low surface-tension liquid, the resulting capillary pumping pressure can be quite high. As a result, when passed through an environment such as the resinous matrix 16, the yarn 14 can wick prodigious quantities of liquid from the surrounding resin, thus causing the yarn 14 to swell. The now swollen yarn 14 then forms mechanical interlocks with the resinous matrix 16 all along its length. This promotes resistance to delamination.
  • Moreover, since at the time of stitching the yarn 14 has not yet become swollen, the stitching process can proceed smoothly, without being hampered by the need to handle swollen yarn 14. It is only after the yarn 14 is safely in place within the composite material 10 that it begins to transition into a state that promotes mechanical interlocking with the surrounding resinous matrix 16.
  • The ability to mechanically interlock with its surroundings is not the only advantage of the swollen yarn 14. Such a yarn 14 also develops an advantageous stress-strain curve. Prior to wicking, the yarn's deformation encompasses a plastic range and an elastic range. Having a plastic range is disadvantageous because a yarn 14 that has been deformed to such an extent does not recover its original shape. On the other hand, after having become swollen, the yarn 14 has essentially no plastic state. Its deformation is primarily elastic. Moreover, the elastic response becomes far less non-linear than it was prior to becoming swollen.
  • Although the yarn 14 will ultimately spend most of its time bonded to the resinous matrix 16 of the composite material 10, it still has to be stitched into place. This is generally carried out with a stitching machine. As a result, it is useful for the yarn 14 to have properties that will enable it to interact smoothly with a typical stitching machine. One way to do this is to use a sizing agent on the yarn 14. Examples of such sizing agents include a friction-reducing film, which can be solid or liquid, and a coating of spalling, such as from graphite. Sizing agents preferably have the property that although they ease passage of the yarn 14 through the stitching equipment, they have little or no effect on the interaction between the yarn 14 and the resinous matrix 16 of the composite material 10.
  • FIG. 2 shows a procedure for manufacturing the reinforced composite material 10 shown in FIG. 1. The procedure begins with forming carbon nanotube fibers with lengths long enough to spin the fibers into yarn 14 (step 18). This can be carried out by forming them at elevated temperatures, such as temperatures above 1000 C, and in particular, at or substantially around 1100 C.
  • The next step is to then spin the yarn 14 (step 20). In principle, one could now proceed directly to stitching the yarn 14 through the composite material (step 32). However, to promote strength, it is useful to promote interaction between the yarn 14 and the resinous matrix 16 (step 22). This can be carried out in one of three ways: by infiltrating the yarn 14 with epoxy (step 24), by infiltrating it with thermoplastic (step 26), or by conditioning the yarn 14 for absorption of the resin (step 28).
  • For mass production, it is useful to also pre-treat the yarn 14 so that a commercial stitching machine can easily stitch it into the composite material (step 30). This involves application of a sizing agent. Finally, the yarn 14 is ready to actually be stitched through the composite material 10 (step 32).

Claims (20)

Having described the invention, and a preferred embodiment thereof, what is claimed as new, and secured by Letters Patent is:
1. A method for manufacturing a manufacture, said method comprising forming carbon nanotubes, spinning said carbon nanotubes into a yarn, and treating said yarn to promote interaction with a resinous matrix.
2. The method of claim 1, further comprising treating said yarn to enable a stitching machine to use said yarn to stitch into a composite material.
3. The method of claim 1, further comprising treating said yarn with sizing.
4. The method of claim 1, further comprising treating said yarn with spalling.
5. The method of claim 1, further comprising treating said yarn with friction-reducing film.
6. The method of claim 1, further comprising treating said yarn with epoxy.
7. The method of claim 1, further comprising treating said yarn with thermoplastic.
8. The method of claim 1, further comprising treating said yarn with a substance selected from the group consisting of PEEK and PEI.
9. The method of claim 1, further comprising treating said yarn with urethane-based plastic.
10. The method of claim 1, further comprising treating said yarn with thermoset material.
11. The method of claim 1, further comprising treating said yarn with polyimide.
12. The apparatus of claim 1, further comprising treating said yarn to promote absorption of resinous material.
13. The method of claim 1, wherein forming carbon nanotubes comprises forming said carbon nanotubes at temperatures higher than 1000 C.
14. A manufacture comprising a yarn, said yarn comprising carbon nanotubes, said yarn having been treated to lo promote interaction with a resinous matrix.
15. The manufacture of claim 14, further comprising a pre-treatment resin that infiltrates said yarn and that fuses with a resinous matrix of a composite material.
16. The manufacture of claim 14, further comprising a plurality of layers having interstitial spaces filled with said resinous matrix, wherein said yarn passes through said layers.
17. The manufacture of claim 14, wherein yarn is swollen with liquid absorbed from said resinous matrix.
18. The manufacture of claim 14, further comprising mechanical interlocks between said yarn and said resinous matrix.
19. The manufacture of claim 14, wherein said carbon nanotubes are single-wall nanotubes.
20. The manufacture of claim 14, wherein said carbon nanotubes are long enough to spin into a fiber.
US15/441,673 2016-02-24 2017-02-24 Yarn for reinforcing composite materials Abandoned US20170241044A1 (en)

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US20070212290A1 (en) * 2005-11-08 2007-09-13 The Regents Of The University Of California Preparation of pile of carbon nanotubes and fiber therefrom
US20100021682A1 (en) * 2008-07-25 2010-01-28 Florida State University Research Foundation Composite material and method for increasing z-axis thermal conductivity of composite sheet material
US20110094777A1 (en) * 2009-10-28 2011-04-28 Xerox Corporation Multilayer Electrical Component, Coating Composition, and Method of Making Electrical Component
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