WO2019195069A1 - Fibres de carbone à rigidité ajustée - Google Patents

Fibres de carbone à rigidité ajustée Download PDF

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Publication number
WO2019195069A1
WO2019195069A1 PCT/US2019/024502 US2019024502W WO2019195069A1 WO 2019195069 A1 WO2019195069 A1 WO 2019195069A1 US 2019024502 W US2019024502 W US 2019024502W WO 2019195069 A1 WO2019195069 A1 WO 2019195069A1
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WO
WIPO (PCT)
Prior art keywords
carbon fiber
coating composition
coated
wax
coated carbon
Prior art date
Application number
PCT/US2019/024502
Other languages
English (en)
Inventor
Shane POLEN
James R. Priest
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.)
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Publication date
Application filed by Ocv Intellectual Capital, Llc filed Critical Ocv Intellectual Capital, Llc
Publication of WO2019195069A1 publication Critical patent/WO2019195069A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
    • C—CHEMISTRY; METALLURGY
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    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/06—Reinforcing macromolecular compounds with loose or coherent fibrous material using pretreated fibrous materials
    • C—CHEMISTRY; METALLURGY
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    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/08—Ingredients agglomerated by treatment with a binding agent
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    • C09D131/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
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    • C09D139/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a single or double bond to nitrogen or by a heterocyclic ring containing nitrogen; Coating compositions based on derivatives of such polymers
    • C09D139/04—Homopolymers or copolymers of monomers containing heterocyclic rings having nitrogen as ring member
    • C09D139/06—Homopolymers or copolymers of N-vinyl-pyrrolidones
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    • C09D191/00—Coating compositions based on oils, fats or waxes; Coating compositions based on derivatives thereof
    • C09D191/06—Waxes
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    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
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Definitions

  • Fiber reinforced composite materials consist of fibers embedded in or bonded to a matrix material with distinct interfaces between the materials. Generally, the fibers are the load- carrying members, while the surrounding matrix keeps the fibers in the desired location and orientation, acts as a load transfer medium, and protects the fibers from environmental damage. Common types of fibers in commercial use today include various types of glass, carbon, and synthetic fibers.
  • Carbon fibers present processing difficulties in many applications, which may lead to slower and more costly product manufacturing. For instance, carbon fibers tend to be limp, lacking inherent stiffness, which causes difficulty in chopping the fibers. Carbon fibers further have low abrasion resistance and thus readily generate fuzz or broken threads and may release particulate material into the air during downstream processing applications. Additionally, due at least in part to their hydrophobic nature, carbon fibers do not interface or wet (i.e., take and hold an aqueous coating) as easily as other reinforcement fibers, such as glass fibers, in traditional resin matrices. Wetting refers to the ability of the resin to uniformly spread over and bond to the fiber surface.
  • coated carbon fiber includes a first coating composition disposed on a carbon fiber and a second coating composition disposed on the carbon fiber.
  • the second coating composition comprises about 0.01 wt.% to about 2.0 wt.% by strand solids of a film former; a processing aid comprising one or more of a wax, a fatty acid, a fatty acid ester, a fatty acid salt, a fatty acid amide, a polymeric lubricant, and a fatty alcohol; and optionally, a compatibilizer comprising one or more of a coupling agent or an antistatic agent.
  • the coated carbon fiber has a total solids content of about 0.01 to about 3.0 wt.%, based on the weight of the coated carbon fiber.
  • the film former comprises one or more of polyvinylpyrrolidone, polyvinyl acetate, polyurethane, and epoxy.
  • the polyvinylpyrrolidone may have a molecular weight of 1,000,000 to 1,700,000.
  • the coated carbon fiber comprises a plurality of fiber bundles, wherein each fiber bundle comprises no more than 12,000 carbon filaments, such as no more than 6,000 carbon filaments, and no more than 3,000 filaments.
  • the coated carbon fiber has a solids content of about 0.05 to about 2.0 wt.%, based on the weight of the coated carbon fiber, such as no greater than about 0.1 to about 1.5 wt.%, based on the weight of the coated carbon fiber.
  • the compatibilizer comprises a coupling agent, comprising one or more of a silicone-based coupling agent, a titanate coupling agent, or a zirconate coupling agent.
  • the compatibilizer comprises an antistatic agent including a quaternary ammonium antistatic agent.
  • the compatibilizer may be present in the coating composition in an amount from about 0.05 wt.% to about 1.0 wt.% solids.
  • the processing aid comprises one or more of a wax, selected from the group consisting of ethylene bis-stearamide wax (EBS), Fischer- Tropsch wax (ET), oxidized Fischer-Tropsch wax (FTO), stearic acid pitch, polyolefin waxes, alcohol wax, silicone wax, petroleum wax, and chlorinated wax.
  • EBS ethylene bis-stearamide wax
  • ET Fischer- Tropsch wax
  • FTO oxidized Fischer-Tropsch wax
  • stearic acid pitch stearic acid pitch
  • polyolefin waxes polyolefin waxes
  • alcohol wax silicone wax
  • petroleum wax and chlorinated wax
  • the coated carbon fiber has a stiffness that is at least 30% higher than an otherwise identical carbon fiber that has not been coated with the secondary coating composition.
  • the coating composition further includes one or more performance additive, selected from the group consisting of silica, nano-silica, silicon carbine, graphene, graphene oxide, graphite, nanoclay, nano-zinc/zinc-oxide, nanoaluminum oxide, core shell rubber, and mixtures thereof.
  • the performance additive may comprise functionalized material, unfunctionalized material, or mixtures thereof.
  • a coated carbon fiber is provided that includes a first coating composition disposed thereon and a secondary coating composition disposed thereon.
  • the coated carbon fiber has a coating solids content thereon of no greater than 2.0 % and wherein the coated carbon fiber has a stiffness that is at least 20% higher than an otherwise identical coated carbon fiber that has not been coated with the secondary coating composition.
  • the secondary coating composition comprises about 0.01 wt.% to about 3.0 wt.% by strand solids of a film former; a processing aid comprising one or more of a wax, a fatty acid, a fatty acid ester, a fatty acid salt, a fatty acid amide, a polymeric lubricant, and a fatty alcohol; and optionally, a compatibilizer comprising one or more of a coupling agent or an antistatic agent.
  • the film former may comprise one or more of polyvinylpyrrolidone, polyvinyl acetate, polyurethane, and epoxy.
  • the polyvinylpyrrolidone may have a molecular weight of 1,000,000 to 1,700,000.
  • a stiffened carbon fiber roving that includes a plurality of carbon fiber bundles comprising no greater than 12,000 carbon filaments.
  • the carbon fiber bundles are coated with a coating composition comprising about 0. 1 to about 4.0 wt.% solids of a film former and about 0.1 to about 3.0 wt.% of a processing aid.
  • the stiffened carbon fiber bundle has a stiffness that is at least 20% higher than an otherwise identical carbon fiber bundle that does not include the coating composition.
  • the carbon fiber bundles comprise no greater than about 6,000 filaments, or no greater than 3,000 filaments.
  • a carbon fiber- reinforced composite includes a plurality of chopped carbon fiber bundles, wherein each fiber bundle comprises no more than 12,000 carbon filaments, and polymer resin material.
  • the chopped carbon fiber bundles comprise a first coating composition and a second coating composition disposed thereon.
  • the second coating composition has a solids content of no greater than 2.0 % and the chopped carbon fibers have a stiffness that is at least 20% higher than an otherwise identical chopped fibers that have not been coated with the secondary coating composition.
  • the carbon fiber reinforced composite has a tensile strength between about 100 and about 300 MPa.
  • the composite has a tensile strength between about 180 MPa and about 220 MPa, a tensile modulus between about 20 GPa and about 40 GPa, a flexural modulus between about 10 GPa and about 50 GPa, and/or a flexural strength between about 250 MPa and about 500 MPa.
  • the reinforcement comprises a sheet molding compound.
  • a sheet molding compound that includes a polymer resin matrix material; and a plurality of coated carbon fiber bundles.
  • the coated carbon fiber bundles comprise a first coating composition and a second coating composition disposed on the carbon fiber bundles.
  • the second coating composition comprises about 0.01 wt.% to about 2.0 wt.% by strand solids of a film former; a processing aid comprising one or more of a wax, a fatty acid, a fatty acid ester, a fatty acid salt, a fatty acid amide, a polymeric lubricant, and a fatty alcohol; and optionally, a compatibilizer comprising one or more of a coupling agent or an antistatic agent.
  • the sheet molding compound has a tensile strength of between about 100 MPa and about 300 MPa, a tensile modulus of between about 20 GPa and about 40 GPa, a flexural modulus of between about 10 GPa and about 50 GPa, and/or a flexural strength of between about 250 MPa and about 500 MPa.
  • a coating composition includes about 0.5 to about 4.0 wt.% solids of a film former comprising one or more of polyvinylpyrrolidone, polyvinyl acetate, polyurethane, and epoxy; about 0.1 to about 3.0 wt.% of the processing aid comprising one or more of a wax, a fatty acid, a fatty acid ester, a fatty acid salt, a fatty acid amide, a polymeric lubricant, and a fatty alcohol; and optionally, at least one compatibilizer, wherein the coating composition has a total solids content of less than 5 wt.%.
  • the composition is an aqueous composition. In other exemplary embodiments, the composition is a nonaqueous composition.
  • the polyvinylpyrrolidone has a molecular weight of 1,000, 000 to 1,700,000.
  • the compatibilizer comprises a silicone-based coupling agent, a titanate coupling agent, or a zirconate coupling agent.
  • the compatibilizer comprises one or more of gluteric dialdehyde, glycoxal, malondialdehyde, succidi aldehyde, phthaladldehyde.
  • the compatibilizer comprises riethylalkyletherammonium sulfate.
  • the compatibilizer may be present in an amount from about 0.01 wt.% to about 1.0 wt.%.
  • the processing aid is present in an amount from about 0.15 wt.% to about 2.7 wt.%.
  • Figure 1 illustrates the results of a“drape test” performed on coated carbon multi- end rovings.
  • wetting refers to the ability of the resin to bond to and uniformly spread over and bond to the fiber surface. Wetting results from the intermolecular interactions between a liquid and a solid surface.
  • the term“tow” refers to a large collection of filaments, which are typically formed simultaneously and optionally coated with a sizing composition.
  • a tow is designated by the number of fiber filaments they contain. For example, a l2k tow contains about 12,000 filaments.
  • the term“roving” means a collection of parallel strands (assembled roving) or parallel continuous filaments (direct roving) assembled without intentional twist.
  • a roving includes both single-end roving and multi -end roving (“MER”).
  • a single-end roving is a single bundle of continuous filaments combined into a discrete strand.
  • a multi -end roving is made up of a plurality of discrete strands, each strand having a plurality of continuous filaments.
  • continuous as used herein in connection with filaments, strands, or rovings, means that the filaments, strands, or rovings generally have a significant length but should not be understood to mean that the length is perpetual or infinite.
  • the present invention relates to methods of imparting increased, tunable stiffness to carbon fibers. While the exemplary embodiments shown and described herein are described in the context of carbon fiber tows, the general inventive concepts are not so limited and instead may be applicable to the decomposition of other types of fibers as well, such as graphite fibers and polymer fibers.
  • Carbon fibers are generally hydrophobic, conductive fibers that have high tensile strength, high temperature tolerance, and low thermal expansion, and are generally light weight, making them popular in forming reinforced composites.
  • carbon fibers may cause processing difficulties, leading to slower and more costly product manufacturing. For instance, conventional carbon fibers typically droop and curve downward due to gravity when held parallel to the ground. Due to this lack of stiffness, the fibers are difficult to chop and utilize in downstream manufacturing processes. Further issues include the tendency for the fibers to break and/or fray during the rubbing, pulling, and spreading motions that occur during processing. Such breaking and fraying may lead to the release of particles into the atmosphere and the formation of“fuzz” on the fibers. In addition to processing difficulties, carbon fibers are hydrophobic and tend to agglomerate, making them harder to wet than hydrophilic glass fibers in traditional matrices.
  • Carbon fibers may be turbostratic or graphitic or have a hybrid structure with both turbostratic and graphitic parts present, depending on the precursor used to make the fibers.
  • turbostratic carbon fibers the sheets of carbon atoms are haphazardly folded, or crumpled together.
  • Carbon fibers derived from polyacrylonitrile (PAN) are turbostratic, whereas carbon fibers derived from mesophase pitch are graphitic after heat treatment at temperatures exceeding 2,200 °C.
  • the carbon fibers of the present invention are derived from PAN.
  • the carbon fibers of the present invention are coated with a first coating composition, such as a sizing composition, to protect the fibers during handing, improve mechanical properties, and/or promote thermal and hydrolytic stability.
  • a sizing composition may also form surface functional groups to promote improved chemical bonding and homogenous mixing within a polymer matrix. Homogenous mixing of the fibers or“wetting” within a polymer matrix material is a measure of how well the reinforcement material is encapsulated by the polymer matrix. It is desirable to have the carbon fibers completely wet with no dry fibers. Incomplete wetting during this initial processing can adversely affect subsequent processing as well as the surface characteristics of the final composite.
  • the sizing composition may be applied to the carbon fibers at any time during the fiber formation process ( e.g ., prior to packaging or storing of the formed fibers) in an amount from about 0.5% to about 5% by weight solids of a fiber, or from about 1.0% to about 2.0% by weight solids of the fiber.
  • the fibers may be coated with the sizing composition after the fibers have been formed (e.g., after the fibers have been packaged or stored).
  • the sizing composition is an aqueous-based composition, such as a suspension or emulsion.
  • the sizing composition may comprise at least one film former.
  • the film former holds individual filaments together to aid in the formation of the fibers and protect the filaments from damage caused by abrasion including, but not limited to, inter-filament abrasion.
  • Acceptable film formers include, for example, polyvinyl acetates, polyurethanes, modified polyolefins, polyesters, epoxides, and mixtures thereof.
  • the film former also helps to enhance the bonding characteristics of the carbon fibers with various resin systems.
  • the sizing composition helps to compatibilize the carbon fibers with an epoxy, polyurethane, polyester, nylon, phenolic, and/or vinyl ester resin.
  • Carbon fibers are frequently supplied in the form of a continuous tow wound onto a reel.
  • Each carbon filament in the tow is a continuous cylinder with a diameter of about 5 pm to about 10 pm.
  • Carbon tows come in a wide variety of sizes, from lk, 3k, 6k, l2k, 24k, 50k, to greater than 50k, etc.
  • the k value indicates the number of individual carbon filaments within the tow. For instance, a l2k tow consists of about 12,000 carbon filaments, while a 50k tow consists of about 50,000 carbon filaments.
  • the carbon must either be manufactured as a fine carbon tow or a larger carbon tow must be split to reduce its filament count.
  • Splitting a high carbon tow (e.g, 24k, 50k, or larger) into smaller splits (e.g, less than l2k) facilitates providing better impregnation with resin and better dispersion when the tow is processed.
  • the carbon fiber tow may be spread to disassociate individual carbon filaments and begin to create a plurality of thinner bundles.
  • the spread carbon fibers may then be pulled under tension to maintain consistent spreading and to further increase the spread between the fibers.
  • a plurality of carbon fibers having widths of about 3/8” to about 1 ⁇ 2” may be pulled along a variety of rollers under tension to form spreads between about 3 ⁇ 4” to about 1 1 ⁇ 2
  • the angles and radius of the rollers should be set to maintain a tension that is not too high, which could pull the spread fibers back together.
  • a surface treatment such as a secondary coating composition
  • the secondary coating may be applied at the time of carbon fiber formation, such as when PAN is converted to carbon fiber.
  • the secondary coating may be applied after the carbon fiber is sized with a sizing composition and at least partially cured.
  • the surface treatment may be applied after carbon fibers are further processed, such as after carbon fibers are spread and/or split into smaller fiber bundles.
  • Prior surface treatments included coating compositions, such as those disclosed in WO2017/062734 and WO2018/187532, each fully incorporated herein by reference.
  • Such coating compositions comprised a minimum solids content of about 2.5 wt.% solids, based on the total solids content of the aqueous composition.
  • the coating composition has a solids content of about 0.1 wt.% to about 5.0 wt.%, or in an amount from about 0.5 wt.% to about 2.0 wt.% active strand solids, or from about 0.5 wt.% to about 1.0 wt.% active strand solids, including all combinations and sub-ranges contained therein.
  • the secondary coating composition comprises less than about 5.0 wt.% solids, or less than about 3.0 wt.% solids, or less than about 2.5 wt.% solids, or less than about 2.0 wt.% solids, or less than about 1.5 wt.% solids, or less than about 1.0 wt.% solids, based on the total solids content of the aqueous composition, including all combinations and sub-ranges contained therein.
  • the secondary coating composition has a solids content of about 0.01 wt.% to about 3.0 wt.%, or in an amount from about 0.05 wt.% to about 2.0 wt.% active strand solids, or from about 0.1 wt.% to about 1.5 wt.% active strand solids, including all combinations and sub-ranges contained therein. In some exemplary embodiments, once applied to the fibers, the secondary coating composition has a solids content of about 1.05 wt.% to about 1.3 wt.%.
  • the secondary coating composition comprises at least one film former.
  • the coating composition may comprise one or more of polyvinylpyrrolidone (PVP), polyvinylacetate (PVA), polyurethane (PU), and epoxy as a film forming agent.
  • Polyvinylpyrrolidone exists in several molecular weight grades characterized by K- value.
  • K- value For example, and not by way of limitation, PVP K-12 has a molecular weight of about 4,000 to about 6,000; PVP K-15 has a molecular weight of about 6,000 to about 15,000; PVP K-30 has a molecular weight of about 40,000 to about 80,000; and PVP K-90 has a molecular weight of about 1,000,000 to about 1,700,000.
  • the film former comprises PVP K-90.
  • the film former may be present in the coating composition in an amount from about 0.1 wt.% to about 4.0 wt.%, or from about 0.25 wt.% to about 2.75 wt.%, or from about 0.5 wt.% to about 1.75 wt.%, based on the total solids content of the aqueous composition, including all combinations and sub-ranges contained therein.
  • the film former may be present in an amount from about 0.01 wt.% to about 2 wt.% by strand solids, or about 0.1 wt.% to about 1.5 by wt.% by strand solids, including all combinations and sub-ranges contained therein.
  • the coating composition additionally includes a compatibilizer.
  • a compatibilizer may provide a variety of functions synergistically between the film former, the carbon fiber, and a resin interface.
  • the compatibilizer comprises a coupling agent, such as a silicone-based coupling agent (e.g silane coupling agents), a titanate coupling agent, or a zirconate coupling agent.
  • Silane coupling agents are conventionally used in sizing compositions for inorganic substrates having hydroxyl groups than can react with the silanol-containing reactive groups. Although such coupling agents have been traditionally used in sizing compositions for glass fibers, alkali metal oxides and carbonates do not form stable bonds with Si-O.
  • silane coupling agents which may be suitable for use in the coating composition, include those characterized by the functional groups acryl, alkyl, amino, epoxy, vinyl, azido, ureido, and isocyanato.
  • Suitable silane coupling agents for use in the coating composition include, but are not limited to, g-aminopropyltriethoxysilane (A-1100), n-trimethoxy-silyl-propyl-ethylene- diamine (A-1120), g-methacryloxypropyltrimethoxysilane (A-174), g- glycidoxypropyltrimethoxysilane (A- 187), methyl -trichlorosilane (A- 154), methyl - trimethoxysilane (A-163), g-mercaptopropyl -trim ethoxy-si lane:(A-l 89), bis-(3-(3-aminopropyltriethoxysilane (A-1100), n-trimethoxy-silyl-propyl-ethylene- diamine (A-1120), g-methacryloxypropyltrimethoxysilane (A-174), g- g
  • [triethoxysilyl]propyl)tetrasulfane (A-1289), g-chloropropyl-trimethoxy-silane (A-143), vinyl- triethoxy-silane (A-151), vinyl-tris-(2-methoxyethoxy)silane (A-172), vinylmethyldimethoxysilane (A-2171), vinyl-triacetoxy silane (A-188), octyltriethoxysilane (A-137), methyltriethoxysilane (A-162), polyazamide silane (A-1387), and gamma- ureidopropyltrialkoxysilane (A-l 160).
  • the compatibilizer comprises a mixture of two or more silane coupling agents.
  • the compatibilizer may include a mixture of aminopropyltriethoxysilane (A-l 100) and one or more of methyl-trimethoxysilane (A-163) and g-methacryloxypropyltrimethoxysilane (A- 174).
  • the compatibilizer includes one or more of polyazamide silane (A- 1387) and gamma- ureidopropyltrialkoxysilane (A-l 160).
  • the compatibilizer includes A-l 100 and A-163 in a ratio of about 1 : 1 to about 3 : 1. In some instances, the compatibilizer includes A-l 100 and A- 174 in a ratio of about 1 : 1 to about 3 : 1.
  • the compatibilizer comprises an organic dialdehyde.
  • exemplary dialdehydes include gluteric dialdehyde, glycoxal, malondialdehyde, sued di aldehyde, phthaladldehyde, and the like.
  • the organic dialdehyde is gluteric dialdehyde.
  • the compatibilizer comprises one or more antistatic agents, such as a quaternary ammonium antistatic agent.
  • the quaternary ammonium antistatic agent may comprise triethylalkyletherammonium sulfate, which is a trialkylalkyetherammonium salt with trialkyl groups, 1-3 carbon atoms, alkyl ether group with alkyl group of 4-18 carbon atoms, and ether group of either ethylene oxide or propylene oxide.
  • triethylalkyletherammonium sulfate is EMERSTAT 6660 A.
  • the compatibilizer may be present in the coating composition in an amount from about 0.05 wt.% to about 5.0 wt.% active solids, or in an amount from about 0.1 wt.% to about 1.0 wt.% active solids, or from about 0.2 wt.% to about 0.7 wt.% active solids. In some exemplary embodiments, the compatibilizer is present in the coating composition in an amount from about 0.3 wt.% to about 0.6 wt.% active solids.
  • the secondary coating composition further includes one or more processing aids, such as one or more of a wax, a fatty acid, a fatty acid ester, a fatty acid salt, a fatty acid amide, a polymeric lubricant, and a fatty alcohol.
  • processing aids such as one or more of a wax, a fatty acid, a fatty acid ester, a fatty acid salt, a fatty acid amide, a polymeric lubricant, and a fatty alcohol.
  • a wax is one or more of a paraffin wax and a non-paraffin wax. Paraffin waxes typically have melting points below 70 °C and have less than 45 carbon atoms.
  • Non-paraffin waxes typically have melting points above 70 °C and have more than 45 carbon atoms.
  • the non-paraffin wax can be one or more of a natural wax, a modified natural wax, a partial synthetic wax, and a full synthetic wax.
  • suitable partial and fully synthetic waxes include ethylene bis-stearamide wax (EBS), Fischer-Tropsch wax (ET), oxidized Fischer-Tropsch wax (FTO), stearic acid pitch, polyolefin waxes such as polyethylene wax (PE), oxidized polyethylene wax (PEO), polypropylene wax, polypropylene/polyethylene wax, alcohol wax, silicone wax, petroleum waxes such as microcyrsatlline wax, and chlorinated wax. Any suitable mixtures of different waxes can also be used.
  • the wax can include a blend of a Fischer-Tropsch wax and a polyethylene wax.
  • the wax is a naturally occurring wax can be derived from a plant, animal or mineral.
  • natural waxes include plant waxes such as candelilla wax, camauba wax, rice wax, Japan wax and jojoba oil; animal waxes such as beeswax, lanolin and whale wax; and mineral waxes such as montan wax, ozokerite and ceresin.
  • the processing aid comprises at least ethylene bistearamide (EBS).
  • EBS is a brittle wax -like solid formed from the reaction of an amine with hydroxystearic acid.
  • the formed hydroxystearamide is a high melting point wax -like material that is extremely resistant to acids and alkalis in contrast to natural and synthetic ester waxes.
  • the processing aid comprises a salt of a fatty acid ester, such as a fatty acid ester derived from a plant or animal.
  • the processing aid may be one or more of a Fischer- Tropsch wax, a polyethylene wax, an oxidized polyethylene wax, and a fatty acid amide.
  • Fatty acid amides are amides produced from the reaction of a fatty acid and an amine.
  • the fatty acid amide can be a monoamide, a substituted amide, a bisamide, a methylol amide, an ester amide, an alkyl urea, and the like.
  • Non-limiting examples of suitable fatty acid amides include oleamide, stearamide, erucamide, behenamide, N-oleylpalmitamide, N-stearylerucamide, ethylene bis-stearamide (EBS), and ethylene bis-oleamide.
  • the processing aid is included in the coating composition in an amount from about 0.01 wt. % to about 3.0 wt.% solids, based on the total weight of the composition. In some exemplary embodiments, the processing aid is included in an amount from about 0.15 to about 2.7 wt.% solids, or from about 0.25 to about 2.5 wt.% solids, or from about 0.3 to about 2.0 wt.% solids, or from about 0.4 to about 1.5 wt.% solids, or from about 0.5 to about 1.0 wt.% solids, based on the total weight of the coating composition, including any combinations and sub-ranges contained therein.
  • the secondary coating composition further includes one or more performance additive to further tune and/or improve mechanical properties of the carbon fibers.
  • the performance additives may include silica, nano-silica, silicon carbine, graphene, graphene oxide, graphite, nanoclay, nano-zinc/zinc-oxide, nanoaluminum oxide, and core shell rubber.
  • the performance materials may comprise functionalized material, unfunctionalized material, or a mixture thereof.
  • the secondary coating composition may be an aqueous coating composition, such that the balance of the composition is water.
  • the composition is non-aqueous, comprising one or more solvents, such as alcohol, or it may include a non- aqueous solvent, comprising a liquid other than water, such as acetone, acetonitrile, dichloromethane ethyl acetate, tetrahyudrofuran, dimethylformamide, and dimethyl sulfoxide.
  • the secondary coating composition has a pH of less than about 10. In some exemplary embodiments, the secondary coating composition has a pH between about 3 and about 7, or between about 4 and about 6, or between about 4.5 and about 5.5.
  • Excess coating composition remaining on the fibers may be removed to at least partially dry the fibers.
  • the fibers may be dried by any method known or practiced in the art.
  • the coated fibers may be dried, such as by pulling the fibers through a dryer, such as an oven.
  • the oven is an infrared or convection oven.
  • the oven may be a non-contact oven, meaning that the carbon fiber tow is pulled through the oven without being contacted by any part of the oven.
  • the oven temperature may be any temperature suitable for properly drying the coating composition on the carbon fibers. In some exemplary embodiments, the oven temperature is from about 230 °F to about 600 °F, or from about 300 °F to about 500 °F.
  • the surface treated fibers may be wound by a winder to produce a high stiffness fiber package, or the fibers may be immediately utilized in a downstream process, such as for compounding with a thermoplastic composition in a long fiber thermoplastic compression molding process, or chopped for use in a compounding process, such as SMC.
  • the tuned stiffness coated fiber tow is utilized to produce a hybrid assembled roving, as described in PCT/US 15/54584, the disclosure of which is incorporated herein by reference.
  • the polymer resin matrix material may comprise any suitable thermoplastic or thermosetting material, such as polyester resin, vinyl ester resin, phenolic resin, epoxy, polyimide, polyurethane, and/or styrene, and any desired additives such as fillers, pigments, UV stabilizers, catalysts, initiators, inhibitors, mold release agents, viscosity modifiers, and the like.
  • the thermosetting material comprises a styrene resin, an unsaturated polyester resin, or a vinyl ester resin.
  • the polymer resin film may comprise a liquid
  • the polymer resin matrix may comprise a paste.
  • the stiffness of the fibers could be increased over an otherwise identical uncoated fiber, while also achieving a reduced stiffness compared to a fiber coated with the coating compositions disclosed in WO2017/062734 and WO2018/187532 (hereinafter referred to as“Comparative Compositions.”
  • the coating composition disclosed herein provides a balance between an appropriate level of stiffness and fiber loft, bundle integrity, and moisture uptake.
  • the secondary coating composition imparts an increased stiffness to the carbon fibers over otherwise identical uncoated fibers, while also achieving a stiffness that is less than that achieved by carbon fibers coated with the Comparative Compositions.
  • carbon fibers that have been coated with the subject coating composition demonstrate at least a 20% increase in stiffness, or at least a 30% increase in stiffness, or at least a 40% increase in stiffness, or at least a 50% increase in stiffness, compared to an otherwise identical carbon fiber that has not been coated.
  • carbon fibers that have been coated with the subject coating composition demonstrate at least a 5% decrease in stiffness, or at least a 10% decrease in stiffness, or at least a 20% decrease in stiffness, or at least a 25% decrease in stiffness, compared to an otherwise identical carbon fiber coated with the Comparative Compositions.
  • the degree of stiffness imparted to the fibers is tunable (i.e., adjustable property).
  • the secondary coating composition reduces the loft in carbon fibers that have been chopped, compared to the loft achieved by fibers coated with the Comparative Compositions.
  • a carbon fiber tow may be split into a plurality of thinner carbon fiber bundles, each comprising no greater than about 15,000 (15k) carbon filaments. Such split carbon fiber tows tend to increase the density of the chop loft.
  • the carbon fiber bundles comprise less than about 12,000 carbon filaments, or less than about 10,000 carbon filaments, or less than about 9,000 carbon filaments, or less than about 8,000 carbon filaments, or less than about 7,000 carbon filaments, or less than about 6,000 carbon filaments, or less than about 5,000 carbon filaments, or less than about 4,000 carbon filaments, or less than about 3,000 carbon filaments, or less than about 2,000 carbon filaments, or less than about 1,000 carbon filaments.
  • the carbon fiber tow comprises from about 1,000 to about 12,000 carbon filaments, or from about 2,000 to about 6,000 carbon filaments, or from about 2,000 to about 3,000 carbon filaments.
  • the carbon fiber bundles have a diameter of about 0.5 mm to about 4.0 mm, or about 1.0 mm to about 3.0 mm.
  • carbon fibers coated with the present secondary coating composition demonstrate reduced water uptake and therefore a lower moisture content.
  • PVP can absorb up to 40% of its weight in atmospheric water.
  • the rate of viscosity increase or“thickening” is driven by moisture availability. Consistency and control of moisture is critical for wetting of the fiber with a resin system prior to high viscosity prevents the wetting the fibers properly. High or varying levels of moisture can cause variation or failure of the system to wet the fibers resulting in poor composite performance.
  • a processing aid reduces the moisture uptake by the coated fiber by at least 10%, or at least 15%, or at least 20%, or at least 30%, or at least 40%, or at least 50%.
  • Table 1 illustrates the moisture content of a carbon fiber coated the coating composition of the present application, compared to the Comparative Compositions. As shown in Table 1, adding wax to the Comparative Compositions did slightly reduce the moisture uptake of the coated fiber. However, when the amount of PVP was reduced by 75% and 0.5 wt.% wax was added, the moisture uptake reduced by over 50%, particularly 58%.
  • the coating composition improves the compatibility of the carbon fibers with a polymeric resin matrix material for composite production. Compatibilizing the carbon fibers with a matrix material allows the carbon fibers to flow and wet properly, forming a substantially homogenous dispersion of carbon fibers within the polymer matrix material.
  • the coating composition also imparts increased cohesion, which allows for improved chopping of the fibers and improved wetting in the consolidation process.
  • the coating composition improves the ability to process a carbon fiber tow by reducing the development of fuzz, fiber breakage, and/or fiber fraying, over otherwise identical carbon fibers that are only coated with a sizing composition, and over otherwise identical carbon fibers that are coating with the Comparative Compositions.
  • the development of fuzz is reduced by at least 25% and in some instances, as much as 130% in carbon fibers coated with the coating composition, compared to otherwise identical fibers coated with the Comparative Compositions.
  • the formation of fuzz works against dispersion of the chopped fibers in a matrix material. Accordingly, by coating the carbon fibers with the coating composition disclosed herein, the formation of fuzz is reduced, which improves fiber dispersion.
  • the coating composition may be adjusted to“tune” the particular properties achieved by the treated fibers.
  • the coating composition may be adjusted to increase or decrease the level of fiber stiffness and/or the level of loft.
  • Such adjustments include increasing or decreasing the solids content (LOI) of the coating composition, exposing the coated fibers to varying temperatures at varying speeds, adjusting the moisture content of the coated fibers, adjusting the angle of contact points that the fibers encounter, changing the particular type of surface treatment applied to the fibers, and/or combining various types of surface treatments.
  • LOI solids content
  • the coated carbon fibers are utilized as large, stiff ribbons (at least 24k) in the formation of composite, such as in the formation of wind turbine blades. Due to the use of the secondary coating compositions disclosed herein, the stiff fiber ribbons have a low solids content (0.5 wt.% to 2.0 wt.% solids), which leads to improved composite properties.
  • the coated reinforcement fibers may then be used in the formation of reinforcement materials, such as reinforced composites, prepregs, fabrics, nonwovens, and the like.
  • the coated fibers may be used in sheet molding compound (“SMC”) applications, for forming an SMC material.
  • SMC sheet molding compound
  • a layer of a polymer film, such as a polyester resin or vinyl ester resin premix is metered onto a plastic carrier sheet that includes a non-adhering surface.
  • Reinforcing fibers are then deposited onto the polymer film and a second, non-adhering carrier sheet containing a second layer of polymer film is positioned onto the first sheet such that the second polymer film contacts the reinforcing fibers and forms a sandwiched material.
  • This sandwiched material is then kneaded to distribute the polymer resin matrix and fiber bundles throughout the resultant SMC material, which may then be rolled for later use in a molding process.
  • wetting is a measure of how well the carbon fiber material is encapsulated by the matrix resin material. It is desirable to have the carbon fiber material completely wet with no dry fibers. Incomplete wetting during this initial processing can adversely affect subsequent processing as well as the surface characteristics of the final composite. For example, poor wetting may result in poor molding characteristics of the SMC, resulting in low composite strengths and surface defects in the final molded part.
  • the SMC manufacturing process throughput such as lines-speeds and productivity, are limited by how well and how quickly the fibers can be completely wet.
  • the SMC material may then be stored for 2-5 days to permit the resin to thicken and mature. During this maturation time, the SMC material increases in viscosity within the range of about 15 million centipoise to about 40 million centipoise.
  • the SMC material may be cut and placed into a mold having the desired shape of the final product.
  • the mold is heated to an elevated temperature and closed to increase the pressure. This combination of high heat and high pressure causes the SMC material to flow and fill out the mold.
  • the matrix resin then goes through a period of maturation, where the material continues to increase in viscosity as a form of chemical thickening or gelling.
  • Exemplary molded composite parts formed using the coated carbon fibers may include exterior automotive body parts and structural automotive body parts.
  • Including carbon fibers that have been coated with the secondary coatings disclosed herein in SMC material allows the productions of SMC material that is at least 3%, or at least 4% stronger (tensile strength) than an otherwise identical SMC material that includes only carbon fibers coated with the Comparative Composition.
  • a carbon fiber-reinforced composite material formed in accordance with the present inventive concepts has a tensile modulus of between about 20 GPa and about 40 GPa, or from about 25 GPa to about 30 GPa including all combinations and sub-ranges contained therein.
  • the carbon fiber-reinforced composite material has a tensile modulus from about 26 GPa to about 32 GPa, or from about 27 GPa to about 30 GPa including all combinations and sub ranges contained therein.
  • a carbon fiber-reinforced composite material formed in accordance with the present inventive concepts has a tensile strength of between about 100 MPa and about 300 MPa, or from about 130 to about 250 MPa, including all combinations and sub-ranges contained therein.
  • the carbon fiber-reinforced composite material has a tensile strength from about 180 MPa to about 220 MPa, or from about 190 MPa to about 208 MPa, including all combinations and sub ranges contained therein.
  • the resulting SMC material has a flexural modulus of between about 10 GPa to about 50 GPa, including about 15 GPa to about 35 GPa, about 20 GPa to about 30 GPa, and about 24 GPa to about 28 GPa, including all combinations and sub ranges contained therein.
  • the resulting SMC material has a flexural strength of about 250 MPa to about 500 MPa, including about 300 MPa to about 400 MPa, about 325 MPa to about 385 MPa, and about 350 to about 375 MPa, including all combinations and sub ranges contained therein.
  • A“drape test” was performed on fibers that were treated with the inventive coating composition and the results are illustrated in Figure 1.
  • the coated roving was then attached to a board and the stiffness was tested based on the level of droop or curvature in the rovings.
  • the coated fibers achieved a balance between a stiff fiber in accordance with the Comparative Compositions (line A) and an uncoated fiber (line B). This balance demonstrates the tunability of the fiber stiffness.
  • the methods may comprise, consist of, or consist essentially of the process steps described herein, as well as any additional or optional process steps described herein or otherwise useful.
  • any particular element recited as relating to a particularly disclosed embodiment should be interpreted as available for use with all disclosed embodiments, unless incorporation of the particular element would be contradictory to the express terms of the embodiment. Additional advantages and modifications will be readily apparent to those skilled in the art. Therefore, the disclosure, in its broader aspects, is not limited to the specific details presented therein, the representative apparatus, or the illustrative examples shown and described. Accordingly, departures may be made from such details without departing from the spirit or scope of the general inventive concepts.

Abstract

L'invention concerne une fibre de carbone revêtue qui comprend une première composition de revêtement disposée sur une fibre de carbone; et une seconde composition de revêtement disposée sur la fibre de carbone. La seconde composition de revêtement comprend environ 0,01 % en poids à environ 2,0 % en poids de matières solides constituées de brins d'une substance filmogène; un auxiliaire de traitement comprenant un ou plusieurs des éléments suivants: une cire, un acide gras, un ester d'acide gras, un sel d'acide gras, un amide d'acide gras, un lubrifiant polymère et un alcool gras; et éventuellement, un agent de compatibilité comprenant au moins un agent de couplage ou au moins un agent antistatique. La fibre de carbone revêtue a une teneur totale en solides d'environ 0,01 à environ 3,0 % en poids, sur la base du poids de la fibre de carbone revêtue.
PCT/US2019/024502 2018-04-05 2019-03-28 Fibres de carbone à rigidité ajustée WO2019195069A1 (fr)

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US201862653027P 2018-04-05 2018-04-05
US62/653,027 2018-04-05
US201962799088P 2019-01-31 2019-01-31
US62/799,088 2019-01-31

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WO2020160378A1 (fr) * 2019-01-31 2020-08-06 Ocv Intellectual Capital, Llc Compositions de revêtement optimisées pour des fibres de carbone
CN113152099A (zh) * 2021-05-14 2021-07-23 哈尔滨工业大学 一种依靠静电作用力优势化地利用仿珍珠层结构改性碳纤维表面的方法
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WO2020160378A1 (fr) * 2019-01-31 2020-08-06 Ocv Intellectual Capital, Llc Compositions de revêtement optimisées pour des fibres de carbone
CN113152099A (zh) * 2021-05-14 2021-07-23 哈尔滨工业大学 一种依靠静电作用力优势化地利用仿珍珠层结构改性碳纤维表面的方法
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