WO2014089001A1 - Câbles et fils de base coupés de renforcement amélioré par du carbone post-revêtu et leurs procédés de formation - Google Patents

Câbles et fils de base coupés de renforcement amélioré par du carbone post-revêtu et leurs procédés de formation Download PDF

Info

Publication number
WO2014089001A1
WO2014089001A1 PCT/US2013/072743 US2013072743W WO2014089001A1 WO 2014089001 A1 WO2014089001 A1 WO 2014089001A1 US 2013072743 W US2013072743 W US 2013072743W WO 2014089001 A1 WO2014089001 A1 WO 2014089001A1
Authority
WO
WIPO (PCT)
Prior art keywords
cer
post
coated
chopped strand
tow
Prior art date
Application number
PCT/US2013/072743
Other languages
English (en)
Inventor
Teresa Wagner
Stephanie Ann RINNE
Scott William SCHWEIGER
William Edwin SMITH
Desmond VANHOUTEN
Leonard J. Adzima
Original Assignee
Ocv Intellectual Capital, Llc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ocv Intellectual Capital, Llc filed Critical Ocv Intellectual Capital, Llc
Publication of WO2014089001A1 publication Critical patent/WO2014089001A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
    • B29C70/06—Fibrous reinforcements only
    • B29C70/10—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres
    • B29C70/12—Fibrous reinforcements only characterised by the structure of fibrous reinforcements, e.g. hollow fibres using fibres of short length, e.g. in the form of a mat
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
    • B29C70/88—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised primarily by possessing specific properties, e.g. electrically conductive or locally reinforced
    • B29C70/882—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts characterised primarily by possessing specific properties, e.g. electrically conductive or locally reinforced partly or totally electrically conductive, e.g. for EMI shielding
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/465—Coatings containing composite materials
    • C03C25/47—Coatings containing composite materials containing particles, fibres or flakes, e.g. in a continuous phase
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C25/00—Surface treatment of fibres or filaments made from glass, minerals or slags
    • C03C25/10—Coating
    • C03C25/48—Coating with two or more coatings having different compositions
    • C03C25/54—Combinations of one or more coatings containing organic materials only with one or more coatings containing inorganic materials only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/005—Reinforced macromolecular compounds with nanosized materials, e.g. nanoparticles, nanofibres, nanotubes, nanowires, nanorods or nanolayered materials
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/36—Inorganic fibres or flakes
    • D21H13/38—Inorganic fibres or flakes siliceous
    • D21H13/40—Inorganic fibres or flakes siliceous vitreous, e.g. mineral wool, glass fibres
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
    • D21H13/36—Inorganic fibres or flakes
    • D21H13/46—Non-siliceous fibres, e.g. from metal oxides
    • D21H13/50—Carbon fibres
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H15/00—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution
    • D21H15/02—Pulp or paper, comprising fibres or web-forming material characterised by features other than their chemical constitution characterised by configuration
    • D21H15/10—Composite fibres

Definitions

  • the general inventive concepts relate generally to carbon enhanced reinforcement (CER) fibers, and more particularly, to post-coated CER tow and post-coated CER chopped strands for improved thermoplastic processing.
  • CER carbon enhanced reinforcement
  • a method for manufacturing a post-coated CER tow and post-coated CER chopped strands with improved properties and dispersibility is also provided.
  • Fibers such as glass fiber, carbon fiber, carbon enhanced reinforcement (CER) fiber, metal fiber, natural fiber, synthetic fiber, or combinations thereof, or the like, are widely used for many different purposes.
  • glass fibers are used as reinforcements in polymeric matrix material to form glass fiber reinforced composites.
  • Carbon nanostructures include carbon nanomaterials, such as carbon nanotubes, for example, that have unique properties that position them for a wide scope of possible applications in suspensions and polymer based solutions, melts, and composites.
  • CNSs are fullerene-related structures of graphite cylinders with unique atomic structures that provide high mechanical properties, namely tensile strength and elastic modulus, excellent thermal and electrical conductivities, and high aspect ratios.
  • One type of CNS includes carbon nanotubes (“CNTs”), which are generally un-branched and may comprise single walled carbon nanotubes (SWCNTs), double walled carbon nanotubes (DWCNTs), and multi- walled carbon nanotubes (MWCNTs).
  • CNSs manifest both electrical and thermal conductivity, high strength, stiffness, and very high aspect ratios. Discovery of these structures has enabled the development of electrically conductive polymeric composites finding use in automotive applications, aerospace applications, battery applications, thermal management applications, electromagnetic interference (EMI) shielding applications, and many other applications.
  • EMI electromagnetic interference
  • CNSs exhibit strong van der Waals forces that attract individual CNSs to one another, causing the CNSs to aggregate into bundles, aggregates, or groupings, making dispersion of the CNSs difficult.
  • CER fibers comprise CNSs grown in situ on fiber substrates, or otherwise affixed, adhered, bonded, or attached to fiber substrates.
  • CNSs grow radially outward from the fiber substrates in a random and structurally entangled manner, forming a percolated network as they grow. Percolation is the formation of well connected pathways of conductive media.
  • the CNSs generally remain directly bonded to the individual fiber substrates throughout processing, such that the fibers act as a scaffold to assist in dispersing CNSs throughout a dispersion media.
  • the CNSs are pre-dispersed over the surface of the fiber substrate. If the CNSs are not adhered to a substrate, the attractive forces of the CNSs tend to cause the CNSs to agglomerate. It is believed that growing the CNSs on the substrate, or otherwise tethering, grafting, bonding the CNSs to the substrate, aids in the dispersion of the CER in a media and thereby the overall formation of a percolated network.
  • CER fibers may be included in matrix materials for formation of composite materials that provide such functions as reinforcement and electromagnetic shielding.
  • Composite reinforcements have been developed where CER fibers are compounded into matrix materials to provide end products, such as EMI shielding.
  • Figures l(a)-(c) illustrate an exemplary process in which a CER tow (1(a)), is post- coated (1(b)), and dispersed in a matrix material (1(c)).
  • Figure 2 illustrates an exemplary post-coating process.
  • Figure 3 illustrates an exemplary process for chopping a post-coated CER tow.
  • Figure 4 illustrates various aspects of an exemplary post-coating process, including an exemplary comb to guide CER fiber tows into a post-coat bath (left top and bottom) and an exemplary stripper die (right top and bottom).
  • Figures 5(a) and (b) illustrate histograms of the average moisture uptake and solids content for various exemplary post-coated CER samples.
  • Figure 6 illustrates a comparison between exemplary in-line dried post-coated CER tow and post-coated CER chopped strands post-coated with both low and high solids loadings.
  • Figure 7 illustrates a comparison between exemplary offline and in-line dried post- coated CER tow and post-coated CER chopped strands.
  • Figures 8 illustrates an exemplary process for chopping a post-coated CER fiber tow.
  • Figures 9-1 1 illustrate the degree of post-coated CER fiber aggregates in various CER composite samples.
  • sizing agent refers collectively to compositions used in the manufacture of fibers as a coating to protect the integrity of fibers, provide enhanced interfacial interactions between a fiber and a matrix material in a composite, and/or alter and/or enhance particular properties of the fibers.
  • fiber or “fiber material” refers to any material which has a fibrous structure as its elemental structural component.
  • the term encompasses fibers, filaments, yarns, tows, tapes, woven and non-woven fabrics, plies, mats, and the like.
  • the general inventive concepts relate to a post-coated CER fiber tow and post-coated CER chopped strand and the process of manufacturing the post-coated CER tow and post- coated CER chopped strand to improve the downstream processing capability of the CER fibers.
  • CER carbon nanostructure
  • CER fiber CER fiber
  • CER strand CER fiber tow
  • CER fiber tow refer collectively to fibers that include carbon nanostructure (CNS) grown in situ thereon. It should be understood that the general inventive concepts relate also to CER fiber which have not had CNSs grown in situ thereon, but rather CER fibers that include CNSs that are affixed, adhered, attached or otherwise bonded thereto.
  • the post coating may be used for a variety of purposes, such as protecting the CNS growth on the fibers, improving the fiowability and processability of the CER fibers in a matrix, while maintaining dispersibility, and/or encapsulating the CNSs for health and safety purposes.
  • the CNSs used in the CER fiber structures may be formed according to any suitable nanostructure forming process, including conventional processes.
  • the forming process may include growing a novel material composed of carbon nanostructures (CNSs) directly on a reinforcing fiber tow through a continuous chemical vapor deposition (CVD) process, which allows the CNSs to take on the dimensionality of MWCNTs.
  • the input reinforcing substrate may comprise any conventional material, such as glass fibers, carbon fibers, and the like.
  • the term "reinforcing" means the substrate may impart some beneficial or otherwise desirable property (e.g., increased strength) to another substrate or material.
  • reinforcing substrates are also contemplated herein such as woven and non-woven fabrics, glass spheres, and the like.
  • reinforcing fibers will be described herein as glass fibers, it is to be appreciated that any conventional reinforcing fiber may be used.
  • the glass may include any type of glass suitable for a particular application and/or desired product specifications, including conventional glasses.
  • Non-exclusive examples of glass compositions include A-type glass fibers, C-type glass fibers, AR-glass fiber, E-type glass fibers, S-type glass fibers, E-CR-type glass fibers (e.g., Advantex® glass fibers commercially available from Owens Corning), R-type glass fibers, wool glass fibers, or combinations thereof, which may be used as the reinforcing fiber.
  • the glass has both a high Young's modulus and high tensile strength, and may maintain some of these properties even in the presence of CNS growth and/or related processing, such as Young's modulus.
  • the input glass is Advantex® glass as a low cost, boron free E-glass and E-CR glass reinforcement.
  • the reinforcing fiber may be fibers of one or more synthetic polymers such as polyester, polyamide, aramid, and mixtures thereof.
  • the polymer strands may be used alone as the reinforcing fiber material, or they can be used in combination with glass fibers such as those described herein.
  • Exemplary structural fibrous materials include glass, in the form of glass fibers; carbon or graphite in the form of carbon or graphite fibers; non-graphite carbon fibers; vitreous carbon fibers; boron monolithic graphite and monolithic non-graphite carbon fibers; silicon; aramid; and other refractory materials.
  • thermoplastic fibrous material may be used.
  • the glass fibers may be formed in any desired shape, such as, for example, circular, oval, ellipse, hollow, flat, rectangular, and square.
  • the glass fibers may be formed having diameters ranging from about 2.0 microns to about 30.0 microns. In some exemplary embodiments, the fibers have a diameter from about 5.0 microns to about 24.0 microns. In some exemplary embodiments, the fibers have a diameter between 9.0 and 13.0 microns. However, it should be understood that any suitable diameter of fiber may be used.
  • the glass fiber input may be continuous or it may be chopped, segmented, or otherwise discontinuous.
  • the fibers are in the form of a continuous fiber tow. If the fibers are chopped, they may be sheared into segments having discrete lengths.
  • the chopped fibers may have a length of approximately 3.0 mm to about 25.0 mm in length. In some additional exemplary embodiments, the fibers have a length from about 20.0 mm to about 35.0 mm.
  • the individual glass fibers are loosely associated into a tow, which is a bundle of twisted or untwisted filaments or untwisted groups of fibers.
  • Tex is a unit of measure for the linear mass density of fibers and is defined as the mass in grams per 1000 meters.
  • the tows may vary in weight and comprise a tex range that is generally between 100 and 9600, and particularly between 300 and 4800. In some additional exemplary embodiments, the tex range is between 400 and 735. If the fibers have a diameter of about 24 micron in a 4000 fiber roving, the tex is 4800. With diameters of about 9 or 10 micron, the tex is 400. In some exemplary embodiments, the tow is a 2000 fiber roving having 400 tex.
  • the tows are wound on winders to collect the continuous glass fiber tows into wound packages, such as doffs or cakes.
  • the wound packages may then be placed in an oven to evaporate the water in the sizing components and further processed in a number of ways.
  • the CNSs may be formed on the fiber substrates according to any suitable nanostructure forming process, including conventional processes, such as, for example, U.S. Patent Number 8,158,217 and U.S. Published Application Number 2010/0279569, each incorporated herein by reference in their entirety.
  • the forming process includes growing CNSs in situ on fiber substrates, or otherwise affixing, adhering, bonding, or attaching the CNSs to fiber tows using a process called continuous chemical vapor deposition (CVD).
  • CVD continuous chemical vapor deposition
  • the CVD process allows the composition and structure of the CNSs to be tuned, selected, or otherwise controlled to tailor the properties of the resulting composite to the specific application needs.
  • Such "tunable" properties include physical properties, such as density and thickness; mechanical properties, such as toughness and isotropy; thermal properties, such as heat stability and conductivity; electrical properties, such as shielding, storing, directing, and absorbing; and durability properties, including corrosion, wear, and fatigue resistance.
  • the CVD process includes catalytic or autocatalytic decomposition of carbon precursor molecules on the surface of a catalyst deposited on a support.
  • the carbon precursor is provided by a carbonaceous gas such as, for example, acetylene, methane, ethylene, nitrogen, and the like.
  • the gas comprises acetylene.
  • This catalytic decomposition may be followed by diffusion of the carbon atoms that are subsequently produced.
  • CNS growth may take places at the location of a catalyst particle.
  • the catalyzed fiber may be fed into an enclosed heated chamber where the CNS growth occurs.
  • the heated enclosed chamber supports an atmosphere including one or more chemical gases.
  • the gas or gas mixture is introduced into the chamber to initiate CNS growth on the fibers.
  • the gas is introduced or heated to a temperature sufficient to cause the carbon atoms from the carbon source to disassociate.
  • CNSs grow directly on a glass fiber as cross-linked structures.
  • the glass fibers with CNSs may be used without purification as a fiber tow, allowing for direct application into an industrial polymer process such as compounding.
  • the CNSs grow radially outward from the glass fibers in a random and structurally entangled manner, forming a percolated network as they grow. Percolation is the formation of well connected pathways of conductive media.
  • the individual CNSs may be branched and/or cross-linked, forming an entangled growth network. The percolation of the CNSs provides enhanced electrical conductivity for greater electrical performance.
  • the CNS branching may stem from catalyst particles that becomes deposited or located on individual CNSs.
  • the CNSs may be CNTs that are single walled, or may include any number of walls, such as between 2 and 12 walls or more.
  • the CNSs include between 4-8 walls. In some exemplary embodiments, the CNSs have 6 +/- 2 walls.
  • the CNSs may vary in size, such as having inside diameters from about 2 nm to about 8 nm. In some exemplary embodiments the CNSs have inside diameters between about 3 nm and about 6 nm. In some exemplary embodiments, the CNSs may have outside diameters between about 5 nm and 20 nm and more. In some exemplary embodiments the CNSs have outside diameters between about 6 to about 10 nm.
  • the CNSs may have lengths from about 5 microns to about 200 microns, and more particularly between 80 and 120 microns.
  • the CNS loading on the fiber substrates, forming the CER fibers may be of any loading level desired for a particular application.
  • the CNS loading on the fiber substrate may be between about 1 and about 50 weight % loading on the fibers.
  • the CNS loading may be between about 10 and about 30 weight % loading on the fibers.
  • the CNS loading may be about 17 to 18 weight % loading.
  • the amount of CNSs grown on the glass fibers may have a large effect on the properties of a downstream article.
  • the CNS loading may be optimized for obtaining the desired properties of the downstream article.
  • the CER tow is post-coated by feeding the CER tow into a bath containing a polymeric post-coat composition.
  • the fibers can be fed into the bath in the form of a CER tow or as individual fibers.
  • the tow or individual fibers may be pulled to and from the bath using a puller, such that the tow or individual fibers are dipped though the bath, which enables each fiber to be generally uniformly coated with the post-coat composition.
  • the post-coat composition may be aqueous or nonaqueous and include a variety of components, such as, for example, film formers, coupling agents, viscosity modifiers, and additives, such as, but not limited to lubricants, surfactants, anti-oxidants, and plasticizers.
  • the particular chemistry selected for the post-coat composition is important, such as not to cause fiber brittleness or other negative fiber properties.
  • the post-coat composition has a solids content of between approximately 0.5% and about 10.0%, however any suitable solids content may be utilized.
  • the film formers for the post-coating composition are generally capable of coating the individual CER fibers or the CER tow as a whole.
  • suitable film formers include, but are not limited to waxes, polyethylene glycols, polypropylene glycols, polycaprolactones, glycidyl ethers, epoxy resins, urethanes, polyester alkyds, amic acid, propylene glycol fumarate, propoxylated bisphenol-A-maleate, propoxylated allyl alcohol- maleate, polyvinyl acetates, olefins, surfactants, maleated polypropylene, low molecular weight polyesters and mixtures thereof.
  • the film former includes one or more of a polyurethane, such as Hydrosize® U6-01 and/or Baybond® PU 401 ; polypropylene; polyethylene glycol ester, such as PEG 400 MO; polyvinylpyrrolidone (PVP), such as PVP K-15, PVP K-30, PVP -90, PVP K-60, and PVP K-120; and epoxy resin, such as EPI-REZTM 351 1.
  • the film former may include one or more surfactant, such as a nonionic surfactant (i.e., Triton X-100), for example.
  • the coupling agent may comprise any coupling agent desired for a particular application.
  • the coupling agent used in the post-coating composition may include one or more of alcohols, amines, esters, ethers, hydrocarbons, siloxanes, silazanes, silanes, lactams, lactones, anhydrides, carbenes, nitrenes, orthoesters, imides, enamines, imines, amides, imides, functionalized olefins and mixtures thereof.
  • the coupling agent is a silane selected from one or more of BM-602 (N-(-aminoethyl)— aminopropylmethyldimethoxysilane), (gamma-
  • the inventive post-coating composition may include additional various additives.
  • the post-coating composition includes a viscosity modifier, including, but not limited to a water soluble polymer, such as an acrylic polymer.
  • an acrylic polymer may include a polyacrylamide, such as Drewfloc 270.
  • the post-coating composition includes a curing agent.
  • the curing agent may comprise dicyandimide (DICY), which is a known curing agent for epoxy resins.
  • the inventive post-coating composition may further include adhesives, such as, for example, an ethylene-vinyl acetate copolymer emulsion (i.e., Airflex® 410).
  • the post-coating composition may further include polyvinylfornmldyde/polyvinylamine or copolymers, which may be obtained from various sources, including Lupamin® 9095, 9050, 9000, 5095, and 1500, for example.
  • the post-coating composition may further include surfactants, such as, for example, non ionic surfactants.
  • exemplary nonionic surfactants may include long chain alcohols, polyoxyethylene glycol alkyl ethers, polyoxypropylene glycol alkyl ethers, glucoside, alkyl ethers, polyoxyethylene glycol alkylphenol ethers, glycerol alkyl esters, polyoxyethylene glycol sorbitan alkyl esters, sorbitan alkyl esters, polyethoxylated tallow amine, cocamide DEA, cocamide MEA, dodecyldimethylamine oxide, poloxamers, polyethyleneamine polyamide salts, ethoxylated acetylenic diols, and octylphenoxypolyethoxyethanol.
  • the inventive post-coat composition comprises one or more of a film former, a coupling agent, and optional additives.
  • the post-coat composition comprises from about 70 to about 99 weight percent film former, about 1 to about 30 weight percent coupling agent and about 0 to about 20 weight percent of optional additives.
  • the post-coat composition includes about 80 to about 90 weight percent film former, about 10 to about 20 weight percent coupling agent, and about 0 to about 10 weight percent additive.
  • the post-coated CER tow maybe chopped to form post-coated CER chopped strands that may be used in downstream processing, such for compounding with a matrix material for use in end use products, such as, electrical and thermal transport applications.
  • the post-coated CER chopped strands may be used to form end products exhibiting EMI shielding, electrostatic discharge (ESD) shielding, lighting strike shielding, radio frequency interface shielding, and the like.
  • Any suitable matrix material may be used, such as, for example, resins (polymers, monomers, or oligomers), both thermosetting and thermoplastic; metals (such as aluminum, titanium, iron, and copper); ceramics (such as silicon carbide, boron carbide, and boron nitride); and cements, or a combination thereof.
  • resins polymers, monomers, or oligomers
  • metals such as aluminum, titanium, iron, and copper
  • ceramics such as silicon carbide, boron carbide, and boron nitride
  • cements or a combination thereof.
  • Thermoplastic resins may include, for example, acrylonitrile butadiene styrene (ABS), polycarbonate (PC), polycarbonate/acrylonitrile butadiene styrene (PC/ABS), polysulfones, polyamides, polyethylenimine (PEI), polycarbonates, polyphenylene oxides, polysulfides, polyether ether ketones (PEEK), poly ether ketone (PEK), polyphenylene sulfide (PPS), polyurethane (PU), polystyrene, polyether sulfones, polyamide-imides, polyetherimides, polyimides, polyarylates, polyphthalamide, acrylic styrene acrylonitrile, polyphenylene ether, polyolefins, polyester, rubber (SBR), butadiene nitrile rubber (BNR), ethylene propylene diene monomer rubber (EPDM), fluoropolymer (FP), liquid
  • the matrix material comprises a thermoplastic resin that is selected from ABS, polycarbonate, polyamides, and combinations thereof.
  • Thermoset resins may include, for example, epoxies, polyesters, phenolics, vinyl esters, polyimides, and the like.
  • CNSs create a "bulky" tow by extending radially from a fiber. Therefore, the overall diameter of the CER tow is larger diameter than a typical glass fiber tow.
  • the CNSs are condensed around the CER tow, as shown in Figure 1(b).
  • the condensed CER fibers may then be chopped and mixed with a matrix material and the CER fibers and associated CNSs are dispersed throughout the matrix, as illustrated in Figure 1(c).
  • applying the post-coat composition to the CER tow improves the processability of the CER chopped strands, at least by condensing the CNSs and allowing for easier handing of the CER chopped strands.
  • Uncoated CER chopped strands are generally difficult to process due to the buildup of fuzz and the limitations and difficulties in feeding the CER chopped strands into downstream processing machines due to the low bulk density of the strands.
  • the term "fuzz,” as used herein, refers to the broken glass filaments that break off from a bundle. Fuzz can accumulate on processing equipment, which may negatively affect downstream processing.
  • the present post-coating process improves the processability and handling of CER chopped strands without reducing CNS dispersibility.
  • the particular chemistry of the post-coat composition may be selected to be at least semi-compatible with the particular matrix material used, which may aid in the dispersion of the CER chopped strands throughout the matrix material.
  • the softening temperature of the post-coat composition is equal to or less than the processing temperature of the matrix material. Therefore, as the post-coated CER chopped strands are compounded with a matrix material, the post-coat composition flows and the CNSs on the CER chopped strands to disperse and un-densify. Therefore, both the CER chopped strands and the CNSs individually are able to disperse in the matrix material as the post-coat composition softens and begins to flow.
  • applying the post-coat composition to the CER tow provides the additional benefit of protecting the individual CNSs formed on a fiber and helping to maintain the CNSs on the fiber during downstream processing.
  • the CER tows and subsequently formed CER chopped strands may be safely handled and easily processed in downstream materials.
  • the CER/matrix material composites may be pelletized to form composite pellets.
  • the composite pellets may be re-processed and/or re-pelletized one or more times to further enhance dispersion, although such reprocessing steps are not necessary with the dispersion of the post-coated CER.
  • the particular CNS loading in a post-coated CER composite may vary depending on the particular application that the composite is to be used for.
  • the post-coated CER/thermoplastic composites have a CNS loading of approximately 1 to approximately 20 weight percent CNS.
  • the CER composite pellets, having about 5 percent by weight CNS may exhibit an EMI shielding effectiveness (SE) between about 30 and 100 dB over a low frequency range (50- 2000 MHz or 0.05-2 GHz) and at a composite thickness of about 3.2 mm, measured using the method in ASTM D4935.
  • SE EMI shielding effectiveness
  • the EMI SE is at least 60 dB in the low frequency range at a thickness of about 3.2 mm.
  • the EMI SE is at least 80 dB in the low frequency range at a thickness of about 3.2 mm.
  • the post-coated CER composites have a resistivity of between less than about 10 " ' " 10 9 oms*cm, and in other exemplary embodiments, the composite has a resistivity about 10 _1 -10 5 oms*cm as determined by the Van der Pauw method. In various exemplary embodiments, the post-coated CER composites, having a 5% CNS loading, have a resistivity of about 0.15 to about 0.4 ohm*cm.
  • the Van der Pauw method includes cutting a square of the composite material and applying silver paint to the corners. A current is then sourced to one side of the square composite by contacting probes to the painted corners. The resulting voltage is then measured using a voltmeter via probes that are connected to the painted edges on the opposite side of the square composite. This process is then repeated for each of the composite's sides. The readings from the sides that are parallel to each other are then averaged. From these averages, the sheet resistance is determined according to the following equation: ⁇ vertical " • ⁇ -horizontal
  • R s is the sheet resistance. When multiplied by the thickness (in cm), the sheet resistance becomes bulk resistivity in ohm*cm.
  • the post-coated CER composite pellets may further exhibit improved mechanical properties. Such properties are dependent upon the particular process steps implemented and also the particular materials used, which will be explained in more detail below.
  • FIG. 2 An exemplary process for producing the inventive post-coated CER tow and post- coated CER chopped strands is shown in Figure 2.
  • the process generally includes growing a plurality of CNSs on an input fiber tow to produce a CER tow, coating the CER tow with a post-coating composition, and chopping the post-coated CER tow to form post-coated CER chopped strands. This process is described in more detail below.
  • the exemplary process is described with respect to exemplary embodiments in which the reinforcement fibers are a single type of glass fibers.
  • glass fibers may be formed by attenuating streams of a molten glass material through a heated bushing to form substantially continuous glass fibers.
  • the continuous fibers are bundled together according to known bundling or packaging methods to form a fiberglass roving or other package, which can in turn be used in the inventive process.
  • the fibers may be coated with a chemical (i.e., size) composition.
  • the size compositions used with CNSs may be silane-free, and include one or more of a film former to provide stiffness and strength, a cationic lubricant that is strongly attracted to glass and protects the glass from abrasion, and a nonionic lubricant that keeps the fibers coated and protected.
  • the fibers may be coated with a catalytic composition that includes one or more of the size ingredients described above and also a catalyst.
  • the catalyst may take on any form, including a solid, liquid, gas, and the like.
  • the size/catalytic composition may be applied to the fibers by any method suitable for the desired CER growth, including kiss roll, dip-coat, slide, or spray application to achieve the desired amount of catalytic composition on the fibers.
  • a fiberglass roving coated with the size/catalytic composition then enters the CER growth processing stage, such that CNSs are grown directly (i.e., in situ) on the surface of the input fiberglass tow.
  • the CER growth processing stage is carried out in a growth chamber and includes various steps that may occur in various sections of the growth chamber.
  • the growth chamber may comprise a single continuous chamber, or it may comprise multiple, connected sub-chambers.
  • the growth processing stage may include a catalyst preparation step, in which the fibers coated with the catalytic composition are heated in a high temperature chamber to remove the size-like components and dry the liquid catalyst.
  • the specific temperature is a function of the particular catalyst disposed on the fibers, but in some exemplary embodiments will be in the range of about 500 °C to 1000 °C.
  • the catalyst preparation step may occur in either a separate unit preceding the growth chamber; within the growth chamber itself; or within proximity to the growth chamber. It should be understood that in various exemplary embodiments, the size-like components need not be removed.
  • the catalyzed glass fiber may be fed into an enclosed heated chamber for the CNS growth.
  • the heated enclosed chamber supports an atmosphere including one or more chemical gases, including a carbon source gas.
  • the gas or gas mixture is introduced into the chamber to initiate CNS growth on the fibers.
  • the gas may include, for example, one or more of acetylene, nitrogen, and hydrogen.
  • the gas comprises acetylene.
  • the gas is introduced at a high temperature sufficient to cause the carbon atoms from the carbon source to disassociate.
  • the carbon source disassociates and carbon nanostructures grow on individual filaments.
  • the process of growing the CNSs on glass fiber structures is based on continuous, rapid, high temperature, catalyzed chemical vapor deposition, which may be tuned to tailor the loading, composition, and structure of the resulting composite to specific application needs.
  • the deposition may be conducted in an enclosed production line so that no particles are released into the environment during production.
  • the CER tow may then be pulled through a post- coat bath containing the post-coat composition, as illustrated in Figure 3.
  • the post-coat composition may be an aqueous or non-aqueous based coating.
  • the post-coat composition may include lubricants, film formers, silanes, and/or additional additives.
  • the particular post- coat composition used depends on the polymer system and performance requirements of the customer.
  • the CER tow may optionally pass over a roller or through grooves, a comb, etc., to help guide the CER fiber tow into the post-coat bath with minimized tangling and/or winding.
  • a comb is provided which includes a number of spaced apart vertical bars that may be located at the entrance to the post-coat bath.
  • the vertical bars may rotate such as to limit the amount of fuzz build-up caused by friction between the tow and the vertical bars. It should be understood that a variety of suitable structures, apparatuses, and articles could be utilized to guide the CER fiber tow into the post-coat bath and the present invention is not limited to the use of the comb illustrated in Figure 4.
  • excess moisture may be removed from the post-coated CER tow through a variety of means, including, for example, passing the post-coated CER tow through one or more forming die, such as, for example, a wire forming die.
  • An exemplary forming die is illustrated in Figure 4 (top). As shown in Figure 4 (bottom right), the forming die may be tapered to remove excess moisture from the CER tow and further consolidate the CER tow by condensing down the individual CNSs.
  • the forming die may be designed to condense the CNSs on the tow, while being careful not to damage the CNSs or remove the individual CNS from the CER tow.
  • the forming die has a particularly diameter and/or particular shape, such that the CER tow exits the stripper die having the approximate diameter and shape of the die.
  • Figure 5(a), (b) illustrates one example of moisture uptake by CER tows.
  • post-coated CER tows were pulled through a forming die, dried, and then weighed. The weight difference between uncoated fibers and post-coated fibers was used to determine the moisture pickup of the post-coated CER fiber tow.
  • the exemplary CER tows tested had an 800 tex and about 17.5 % CER loading in the post-coat composition.
  • the samples provided an average moisture content of 70.6% with a forming die diameter of 78 mils ( Figure 5(a)).
  • the solids content on the fibers was averaged at 9.4% ( Figure 5(b)).
  • a forming die diameter of 78 mils was used; however, forming dies of various suitable diameters may be used.
  • the fibers may be dried to obtain a desired final moisture content.
  • the drying may occur in-line, off-line, or a combination of both in-line and off-line.
  • water from the post-coat composition is driven off a CER tow in an oven, such as a convection oven, or other heating apparatus, such that a final coating is formed on the CER tow.
  • the final coating comprises an at least partially dried and/or cured post-coat composition.
  • the CER tow may be pulled through an in-line drying oven that is heated to any desired temperature for a particular result.
  • the oven temperature is between approximately 350 °F-700 °F, particularly about 600 °F.
  • the drying step occurs off-line in an oven once the CER tow has been wound wet into a spool.
  • the wet- wound CER spool may be placed in an oven and heated at any desired temperature, such as between approximately 100-130 °C for a period of time determined to produce a desired moisture content.
  • the CER tow may also be partially dried in-line and then wound and further dried off-line. Drying the fiber tow in-line prior to winding may allow the use of a post-coating with a higher solids content (e.g. 10-15%), which has been shown to provide a better coating of a CER tow and also reduced the fuzz that is produced.
  • Winding a wet CER tows post-coated with a composition having a high solids content may cause excessive stickiness, such that the tows stick together during winding. Pulling apart CER tows that have excessive stickiness may create fuzz on the tow. Therefore, in-line drying a CER tow post- coated with a high solids content composition may produce a post-coated CER tow with a better coating with less fuzz.
  • post-coat compositions with differing solids content were used to post-coat CER tows and the coated tows were dried using an in-line drying process. Some of the samples were then chopped to produce post-coated CER chopped strands.
  • One exemplary post-coat composition had a low solids content and the other exemplary composition included a solids content that was increased by a factor of 8.
  • the post-coated CER tow produced using the post-coat composition with a lower solids content was less condensed than the tow coated with the composition having a higher solids content (Figure 6, right column).
  • compositions with the lower solids content were unable to fully coat the fibers and generated fuzz and dust due to the breakage of glass filaments and CNSs falling off during processing, making downstream processing of the chopped strands difficult.
  • a higher solids content improves the quality of the coating on the fibers, reduces the fuzz and dust produced, and improves the overall chopped strand quality.
  • Whether a post-coated CER tow is dried off-line or inline may also effect the cross- sectional size and shape of the resulting tow.
  • tows that are wound wet and dried offline may have a wide and flattened shape, due to winding and compressing the fibers while the post-coat composition is wet.
  • tows that formed by the forming die and inline dried may be more consolidated and round, since the post-coat composition is able to dry prior to winding the fiber.
  • a wide flat fiber tow may have lower bulk density, which may affect the ability of chopped fibers to flow in downstream processing.
  • the in-line drying process produces a more consolidated strand and a higher bulk density chopped CER fiber that is more likely to flow in downstream processing (See, e.g., Figure 7).
  • passing a post-coated CER tow through a forming die and then inline drying the tow may increase package density by about 2.5 times over off-line drying. Therefore, in-line drying a CER tow post-coated with a high solids content composition produced the most condensed chopped strands.
  • the post-coated CER tow exits the in-line drying oven, if present, and is wound into one or more packages of post-coated CER fibers.
  • the CER tow may optionally be passed through guide eyes to keep the tow(s) straight and separate, in the case of multiple tows, for winding.
  • the winder may be a single winder, or may include multiple winders, used in conjunction.
  • the throughput of the post-coating process was doubled by including two winders in the process.
  • Another processing variable that may improve throughput includes reducing breakouts, such as by utilizing a bath with a shallower angle to reduce abrasion, reducing the tension on the fiber tow as it moves through the process (while maintaining some tension), and changing the knot type when stringing the tow.
  • the winder may comprise any winder generally used in the art, such as an inside pull winder that is built on a rubber bladder, or an outside pull winder that is built on a cardboard core.
  • the post-coated CER tow is wound on an inside-pull winder creating a package of up to about 12" outer diameter.
  • the package may be effectively stored and/or used for downstream processing.
  • the CER fiber spools can be placed together for collective transfer away from the growth line.
  • the tow may be fed directly into a chopper for the formation of a plurality of post-coated CER chopped strands.
  • the CER package is unwound and pulled through a chopper, as exemplified in Figure 8.
  • the chopper may comprise any conventional cutting means, such as, for example a blade cutter head that includes razor blades inserted into slots positioned a distance corresponding to the length of a desired chopped strand.
  • the post-coated CER chopped strands produced may be of any length desired for a particular application, such as, for example, from about 1/8 inch to about 1 inch.
  • the chopping may take place in-line, which eliminates the winding step.
  • removing the winding step allows for a more consistent output, which may provide a higher process yield of choppable material.
  • multiple tows may be chopped at once, which may increase productivity, such as, for example, increasing the CER chopped strands produced.
  • the post-coated CER chopped strands are implemented in downstream processes, such as mixing the chopped strands with a matrix material to produce a CER/matrix material composite.
  • the post- coated CER chopped strands are intimately mixed with the matrix material by a compounding process.
  • the post-coated CER chopped strands are fed into a compounding extruder such as, for example, a twin-screw extruder. As the post-coated CER chopped strands are introduced into a heated, polymer filled twin screw extruder barrel, the post-coating on the chopped strands softens and begins to flow.
  • the CNSs both on and off of the strands become intimately mixed and dispersed within matrix material. Therefore, as the post-coated CER chopped strands are mixed with the matrix material, a sufficient percentage of the matrix material includes the CNS material.
  • the thermoplastic matrix may be pelletized to form CER matrix material composite pellets.
  • the composite pellets may be reprocessed and/or re-pelletized one or more times to further enhance dispersion, although such reprocessing steps are not necessary with the improved dispersion of the CER.
  • the pelletized CER composite pellets may further be "let down," which means diluting the composites with additional matrix material for use with different applications.
  • the diluting matrix material may be of the same or a different type of matrix material that is initially included within the pellet.
  • the CER composite pellets may be concentrated with CNSs, such as about 5 to about 25 weight percent CNSs, and in some exemplary embodiments, about 8 to about 12 weight percent CNSs in the pellet.
  • the CER composite pellets may then be let down, or diluted, to lower the CNS levels. In some exemplary embodiments, the CER composite pellets are diluted to levels ranging from about 10% CNSs to less than l% CNSs.
  • Downstream products such as EMI shielding articles, may be produced by processing the pelletized CER thermoplastic composite through any desired composite processing means.
  • the composite may further be molded into a desired shape for a particular application.
  • Example 1 Post-Coat Compositions and Bulk Density.
  • Exemplary post-coat compositions having different chemistries were produced and used to post-coat exemplary CER tows.
  • the exemplary tows were 800 tex and comprising 10 micron glass fibers having an 18% CNS loading.
  • the exemplary post-coated CER tows were examined for both the coating on the stand and the bulk density of the post-coated tow. Table 1, below, lists the exemplary post-coat compositions and resulting properties.
  • Table 1 Exemplary post-coat compositions.
  • Higher bulk density samples generally represent a more consolidated post-coated CER tow.
  • Exemplary post-coats 142B and 142 A include only film formers and are void of any silane. These compositions illustrate how the coating on the strands may affect the resulting bulk density of the CER tow. For instance, Trial 2 included an 11.2 weight % coating on the strands compared to Trial 1 with a 4.4 weight % coating. Trial 2 resulted in a higher bulk density than Trial 1 , which indicates that the amount of post-coating on the strands may influence the resulting bulk density. Additionally, Trial 3 includes the addition of a silane and has a similar coating percentage on the strands. However, Trial 3 achieves a higher bulk density, indicating that the addition of a silane is important in achieving a high bulk density.
  • Trials 4-6 further exemplify the influence that the amount of post-coating may have on the bulk density of a resulting post-coated strand.
  • Trial 4 included only a 1.7 weight % coating and demonstrated the lowest bulk density at 0.1 g/ml, while Trial 5, with a 6.8 weight % coating resulted in a bulk density of 0.18 g.ml and Trial 6, with a 13.5 weight % coating resulted in the highest bulk density, at 0.21 g/ml.
  • Trials 7 and 8 illustrate the importance of selecting the proper film former when optimizing bulk density.
  • Trial 7 includes an aqueous polyurethane dispersion as the film former and
  • Trial 8 includes an aqueous polyurethane solution.
  • Trial 7 used a higher weight percent of post-coating on the strands, Trial 8 nonetheless resulted in a higher bulk density. Therefore, it is believed that using an aqueous polyurethane solution may result in a higher bulk density than using an aqueous polyurethane dispersion. This difference may be attributed to the particles present in the dispersion, which may make it more difficult for the polyurethane to penetrate into the CNS, while a solution may better wet the CNS.
  • coatings comprising polyurethane dispersion are still acceptable for use in the inventive post- coat composition.
  • Trials 6 and 8 further illustrate the affect that the selection of silane may have on the resulting bulk density of a post-coated CER tow.
  • Trial 6 includes a 3-aminopropyl methyldiethoxy silane
  • Trial 8 includes a gamma-aminopropyltriethoxysilane.
  • Each post-coat composition included the same type of film former and included the silane and film former in the same amounts. Therefore, the only difference was the type of silane used and the amount of coating on the strands.
  • Trial 6 had a higher coating percentage at 13.5 weight %
  • Trial 8 using the gamma-aminopropyltriethoxysilane, resulted in a higher bulk density than Trial 6.
  • Exemplary post-coat compositions were prepared using different chemistries and used to post-coat CER tows.
  • the exemplary tows were 800 tex and comprised 10 micron glass fibers having an 18% CNS loading.
  • the post-coated CER tows were then chopped and compounded into various matrix materials to form CER composites. Each composite was about 0.125 inches thick and the EMI shielding Effectiveness (EMI SE) was measured according to ASTM 4935.
  • the EMI SE listed below is an average from the frequency range of 0.5 to 2 GHz.
  • the particular post-coat formulations and matrix materials used are listed below in Table 2.
  • the EMI SE of the CER composites listed above correlates to the overall dispersion of the CNS throughout the thermoplastic material. The higher the EMI SE, the better dispersion achieved by the CNS in the composite.
  • Trials 9-10 include post- coated CER composites in polyamide 6,6.
  • the post-coat of Trial 9 comprises an aqueous polyamide dispersion film former and an aminopropyl methyldiethoxy silane coupling agent.
  • the post-coat of Trial 10 includes a non-ionic polypropylene emulsion film former and an N- (-aminoethyl)--aminopropylmethyldimethoxysilane coupling agent.
  • each composite demonstrates EMI SE that is comparable to that of an un-post- coated CER composite in PA-6,6 (Trial 11). Accordingly, the post-coat compositions in Trials 9 and 10 are believed to maintain the dispersion ability of un-coated chopped strands.
  • Trials 12-13 comprise post-coated CER composites formed with polypropylene.
  • the post-coat composition of Trial 12 included an aqueous polyurethane solution and a gamma - Aminopropyltriethoxysilane coupling agent.
  • the post-coat composition of Trial 13 included a non-ionic propylene emulsion and an N-(-aminoethyl) ⁇ aminopropylmethyldimethoxysilane coupling agent.
  • Trials 15-17 were formed using a high density polyethylene matrix material.
  • Trial 15 was formed using a post-coat composition comprising an aqueous polyurethane solution film former and a gamma - aminopropyltriethoxysilane coupling agent.
  • Trial 16 was formed using a nonionic polypropylene emulsion film former and an N-(-aminoethyl)-aminopropylmethyldimethoxysilane coupling agent.
  • Trial 17 was formed using a non-ionic polyethylene emulsion film former and a gamma - aminopropyltriethoxysilane coupling agent.
  • Trials 15-17 demonstrate comparable bulk density, although only Trial 16 shows comparable EMI SE to that of the un-coated CER/high density polyethylene composite (Trial 18).
  • Trial 15 demonstrated slightly better shielding results than Trial 17, which indicates that, since the post-coat compositions included the same silane, a post-coat composition comprising an aqueous polyurethane film former is believe to achieve better dispersion in high density polyethylene than that with a non-ionic polyethylene film former.
  • Exemplary post-coat compositions were prepared using different chemistries and used to post-coat CER tows.
  • the exemplary tows were 800 tex and comprised 10 micron glass fibers having an 18% CNS loading.
  • the post-coated CER tows were then chopped and injection molded with a polyamide 6,6 material to form a 6" x 6" x 1/8" composite panel.
  • Three exemplary panels were prepared. The exemplary panels were tested for dispersion performance using the Aggregate Measurement Technique, which is described below.
  • the first panel was formed using uncoated CER chopped strands. Each of the remaining two panels included post-coated CER chopped strands.
  • the particular post-coat compositions used are displayed below in Table 3.
  • a 35 mm diameter piece was cored from each sample at the same location on the composite and the samples were polished to a 6 micron diamond finish. Approximately 1 mm portion of the top surface was removed from each sample and these portions were analyzed using reflected light stereoscope. The percentage in each portion that was covered by CER fiber aggregates larger than 175 micrometers in diameter were recorded. Additionally, the shielding effectiveness of each sample was measured according to ASTM D4935 on 0.125 inch thick injection molded parts at a frequency between 0.5 and 2 GHz. The results are listed in Table 3, above.
  • the composite formed using uncoated CER chopped strands demonstrated about 4% CER fiber aggregates and an EMI shielding effectiveness of 48 dB ( Figure 9).
  • the composite formed using CER chopped strands that had been post- coated with the 154E post-coat composition similarly demonstrated 4% CER fiber aggregates and an improved EMI shielding effectiveness of 48 dB ( Figure 11).
  • the composite formed using CER chopped strands post-coated with the 162A post-coat composition demonstrated a higher percentage of CER fiber aggregates, at 13% and demonstrated low EMI shielding effectiveness at 34 dB ( Figure 10). Therefore, the particular make up of the post-coat composition is important for achieving dispersion comparable to that achieved by non-post-coated CER chopped strands and particularly, a CER fiber aggregate percentage of less than 10%.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Nanotechnology (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Geochemistry & Mineralogy (AREA)
  • General Chemical & Material Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Mechanical Engineering (AREA)
  • General Physics & Mathematics (AREA)
  • Textile Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Reinforced Plastic Materials (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un fil de base coupé de renforcement amélioré par du carbone post-revêtu (« CER ») comprenant un fil de base coupé CER qui comprend au moins une fibre de renforcement ayant une pluralité de nanostructures de carbone (« CNS ») disposées sur celui-ci. Les CNS s'étendent à partir de la ou des fibres de renforcement. Le renforcement amélioré par le carbone post-revêtu comprend de plus une composition de post-revêtement revêtant de façon substantielle le fil de base coupé CER, formant un fil de base coupé CER post-revêtu.
PCT/US2013/072743 2012-12-05 2013-12-03 Câbles et fils de base coupés de renforcement amélioré par du carbone post-revêtu et leurs procédés de formation WO2014089001A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US201261733672P 2012-12-05 2012-12-05
US61/733,672 2012-12-05

Publications (1)

Publication Number Publication Date
WO2014089001A1 true WO2014089001A1 (fr) 2014-06-12

Family

ID=50030442

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2013/072743 WO2014089001A1 (fr) 2012-12-05 2013-12-03 Câbles et fils de base coupés de renforcement amélioré par du carbone post-revêtu et leurs procédés de formation

Country Status (1)

Country Link
WO (1) WO2014089001A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108291072A (zh) * 2015-10-08 2018-07-17 Ocv智识资本有限责任公司 用于增强纤维的后-涂布组合物
CN109516698A (zh) * 2018-11-29 2019-03-26 巨石集团有限公司 一种外退拉挤法增强聚丙烯用玻璃纤维直接纱浸润剂及其应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008085634A1 (fr) * 2007-01-03 2008-07-17 Lockheed Martin Corporation Fibre infusée en ntc et procédé de production de celle-ci
US20100143701A1 (en) * 2003-06-16 2010-06-10 Jiang Zhu Fiber-Reinforced Polymer Composites Containing Functionalized Carbon Nanotubes
US20100270069A1 (en) * 2009-04-24 2010-10-28 Lockheed Martin Corporation Cnt-infused emi shielding composite and coating
US20100279569A1 (en) 2007-01-03 2010-11-04 Lockheed Martin Corporation Cnt-infused glass fiber materials and process therefor
WO2010144161A2 (fr) * 2009-02-17 2010-12-16 Lockheed Martin Corporation Composites comprenant des nanotubes de carbone sur fibres

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100143701A1 (en) * 2003-06-16 2010-06-10 Jiang Zhu Fiber-Reinforced Polymer Composites Containing Functionalized Carbon Nanotubes
WO2008085634A1 (fr) * 2007-01-03 2008-07-17 Lockheed Martin Corporation Fibre infusée en ntc et procédé de production de celle-ci
US20100279569A1 (en) 2007-01-03 2010-11-04 Lockheed Martin Corporation Cnt-infused glass fiber materials and process therefor
US8158217B2 (en) 2007-01-03 2012-04-17 Applied Nanostructured Solutions, Llc CNT-infused fiber and method therefor
WO2010144161A2 (fr) * 2009-02-17 2010-12-16 Lockheed Martin Corporation Composites comprenant des nanotubes de carbone sur fibres
US20100270069A1 (en) * 2009-04-24 2010-10-28 Lockheed Martin Corporation Cnt-infused emi shielding composite and coating

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108291072A (zh) * 2015-10-08 2018-07-17 Ocv智识资本有限责任公司 用于增强纤维的后-涂布组合物
CN109516698A (zh) * 2018-11-29 2019-03-26 巨石集团有限公司 一种外退拉挤法增强聚丙烯用玻璃纤维直接纱浸润剂及其应用
CN109516698B (zh) * 2018-11-29 2022-02-01 巨石集团有限公司 一种外退拉挤法增强聚丙烯用玻璃纤维直接纱浸润剂及其应用

Similar Documents

Publication Publication Date Title
EP2900473B1 (fr) Matériaux composites formés par mélange par cisaillement de nanostructures de carbone et procédés apparentés
JP5662156B2 (ja) ガラス長繊維強化熱可塑性組成物の製造方法
KR20120101406A (ko) Ｃｎｔ 주입 금속 섬유 물질 및 그 방법
US20110297892A1 (en) Cnt-infused fibers in thermoplastic matrices
KR20170066519A (ko) 하이브리드 강화 조립체들
KR20120036890A (ko) 복합재 섬유에 나노입자의 결합
CA2750386A1 (fr) Materiaux en fibres de verre impregnes de nanotubes de carbone et procede associe
KR20120099690A (ko) Ｃｎｔ 주입 아라미드 섬유 물질 및 그 방법
WO2011053457A1 (fr) Matières fibreuses céramiques imprégnées de ntc et procédé correspondant
EP2768770A1 (fr) Systèmes et procédés pour la production continue de nanostructures de carbone sur des substrats réutilisables
KR20180067592A (ko) 강화 섬유용 후-코팅 조성물
WO2017145883A1 (fr) Matériau composite renforcé par fibres discontinues
JP2018008879A (ja) ガラス繊維ストランドおよびそれを含む強化された製品
US9506194B2 (en) Dispersion of carbon enhanced reinforcement fibers in aqueous or non-aqueous media
WO2014089001A1 (fr) Câbles et fils de base coupés de renforcement amélioré par du carbone post-revêtu et leurs procédés de formation
KR20190133764A (ko) 강성이 개선된 보강 섬유
JP5304086B2 (ja) 抄紙基材の製造方法
JP5304085B2 (ja) 抄紙基材の製造方法
WO2023089969A1 (fr) Procédé de production de stratifil à plis multiples, stratifil à plis multiples et corps moulé en résine renforcé par des fibres de verre
JP6715656B2 (ja) 易開繊性繊維材料及びその製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 13826675

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 13826675

Country of ref document: EP

Kind code of ref document: A1