US3914504A - Sized carbon fibers - Google Patents

Sized carbon fibers Download PDF

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Publication number
US3914504A
US3914504A US402493A US40249373A US3914504A US 3914504 A US3914504 A US 3914504A US 402493 A US402493 A US 402493A US 40249373 A US40249373 A US 40249373A US 3914504 A US3914504 A US 3914504A
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bisphenol
weight
fiber
diglycidyl ether
carbon fibers
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Expired - Lifetime
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US402493A
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Winfred E Weldy
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Hercules LLC
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Hercules LLC
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Priority to US402493A priority Critical patent/US3914504A/en
Priority to CA208,181A priority patent/CA1033232A/en
Priority to JP10126374A priority patent/JPS5715229B2/ja
Priority to DE19742446097 priority patent/DE2446097A1/de
Priority to IT27908/74A priority patent/IT1022474B/it
Priority to GB4235574A priority patent/GB1454424A/en
Priority to FR7433424A priority patent/FR2246663B1/fr
Priority to US05/554,998 priority patent/US3957716A/en
Application granted granted Critical
Publication of US3914504A publication Critical patent/US3914504A/en
Priority to MY1977237A priority patent/MY7700237A/xx
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F11/00—Chemical after-treatment of artificial filaments or the like during manufacture
    • D01F11/10—Chemical after-treatment of artificial filaments or the like during manufacture of carbon
    • D01F11/14—Chemical after-treatment of artificial filaments or the like during manufacture of carbon with organic compounds, e.g. macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2913—Rod, strand, filament or fiber
    • Y10T428/2918—Rod, strand, filament or fiber including free carbon or carbide or therewith [not as steel]

Definitions

  • This invention relates to protective sizing compositions for carbon fibers and in particular to protective sizing compositions for'carbon fibers based on certain epoxy compounds.
  • carbon fibers is used in this application in its generic sense and includes both graphite fibers and amorphous carbon fibers.
  • Graphite fibers are-defined herein as fibers whichconsist essentially of carbon and have a predominate X-ray diffraction'pattern,characteristic of graphite.
  • Amorphous carbon fibers are defined-asfibers inwhich the bulk of the fiber weight can be attributed to carbon and which exhibit an essentially amorphous X-ray diffraction pattern.
  • Carbon fibers can be prepared ,by known process from polymeric fibrous materialssuch as polyacrylonitrile, polyvinyl alcohol, pitch, natural and regenerated cellulose, which processes include the steps of carbonizing or graphitizingthe fibers.
  • Carbon fibers are generally fragile and subject to abrasion during handling. It has now been discovered that sizing compositions based on certain epoxy compounds protect carbon fibers against suchv damage.
  • carbon fibers When carbon fibers are to be used in preparing composite structures with resin matrixsystems they are frequently subjected to a surface pretreatment to improve the adhesion between the carbon fibers and the resin matrix.
  • the fiber surface is usually oxidized in such a pretreatment, for example by reaction with an oxidizing'agent.
  • the carbon fiber can be oxidiz ed by electrolytic treatment. using an electrolyte which will generate nascent oxygen at the, surface of the carbon fiber during the electrolysis process.
  • the sizing compositions of this invention do not detract from the adhesioni mprovement of such surface treated fibers.
  • carbon fibers coated with a sizing composition comprising lan epoxy compound, selected from the group consisting of polyglycidyl ethers, cycloaliphatic polyepoxides and mixtures thereof.
  • the sized carbon fibers are compatible with epoxy resin matrix systems used to prepare composite structures. The size can be applied to untreated or surface pretreated carbon fibers to protect them against abrasion damage.
  • Polyglycidyl ethers which can be used,-in accordance with this invention, as a protective size for carbon fibers include diglycidyl ethers, triglycidyl ethers, tetraglycidyl ethers and higher polyglycidyl ethers. Mixtures of any of the polyglycidyl ethers can also be used.
  • diglycidyl ethers that can be employed include diglycidyl ether; diglycidyl ether of 1,3- butanediol; 2,6-diglycidyl phenyl glycidyl ether; 1,8- bis(2,3-epoxypropoxy)octane; l,3-bis(2,3-epoxypropoxy)benzene; l,4-bis( 2,3-epoxypropoxy)benzene; l,3-bis(4,5-epoxypentoxy)-5-chlorobenzene; 4,4 bis(2,3-epoxypropoxy)diphenyl ether; 2,2-bis(2,3- epoxypropoxyphenyl)methane; and 2,2-bis[p-(2,3- epoxypropoxy)phenyl] propane, i.e., the diglycidyl ether of bisphenol A.
  • Illustrative triglycidyl ethers that can be employed include triglycidyl ethers such as the triglycidyl ethers of trihydric alcohols such as glycerol, l, l,l-tri(hydroxymethyl)propane, 1,2,6-hexanetriol and the higher alcohols; and the triglycidyl ethers of trihydric phenols, such as phloroglucinol, the trihydroxydiphenyl methanes and propanes, the trihydroxyaminophenols, the trisphenols; 2,2[2,4,4'-tris(epoxypropoxy)diphenyl]- propane; l, 1 -bis( glycidyloxymethyl )-3 ,4-epoxycyclohexane; and N,N,Otris(epoxypropyl) p-aminophenol.
  • trihydric alcohols such as glycerol, l, l,l-
  • Illustrative tetraand higher polyglycidyl ethers that can be employed include tetraglycidyl ether of p,p'diaminodiphenylmethane and epoxidized novolac compounds.
  • Cycloaliphatic polyepoxides which can be used to provide a protective size on carbon fibers in accordance with this invention include bis-2,3-epoxycyclopentyl ether; I,4-bis(2,3-epoxypropoxy)cyclohexane; l,4-bis(3,4-epoxybutoxy)-2-chlorocyclohexane; the di(epoxycyclohexanecarboxylates) of aliphatic diols; the oxyalkylene glycol epoxycyclohexanecarboxylates; the epoxycyclohexylalkyl epoxycyclohexanecarboxylates; epoxycyclohexylalkyl dicarboxylates; epoxycyclohexylalkyl phenylenedicarboxylates; bis(3,4-epoxy- 6-methylcyclohexylmethyl) diethylene glycol ether; dicyclopentadiene dioxide; bis(2,3-epoxycyclopen
  • di(epoxycyclohexanecarboxylates) of aliphatic diols which can be employed include the bis(3,4-epoxycyclohexanecarboxylate) of l,5-pentanediol, 3,-methyl-l ,S-pentanediol, 2-methoxymethyl+ 2,4-dimethyl-l,S-pentanediol, ethylene glycol, 2,2- diethyl-l,3-propanediol, l,6-hexanediol and 2-butene- 1,4-diol.
  • oxyalkylene glycol epoxycyclohexanecarboxylates which can be employed include bis(2- ethylhexyl-4,5- epoxycyclohexane-l,2-dicarboxylate) of dipropylene glycol, bis(3,4-epoxy-6-methylcyclohexanecarboxylate) of diethylene glycol and bis(3,4-epoxycyclohexanecarboxylate) of triethylene glycol.
  • epoxycyclohexylalkyl epoxycyclohexanecarboxylates which can be employed include 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-l-methylcyclohexylrnethyl 3,4 epoxy-l-methylcyclohexanecarboxylate, 3,4-epoxy-2- methylcyclohexylmethyl 3,4-epoxy-2-methylcyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl 3,4-epoxy-6-methylcyclohexanecarboxylate, (1- chloro-3,4-epoxycyclohexan-1-yl) methyl l-chloro- 3 ,4-epoxycyclohexanecarboxylate, l-bromo-3 ,4- epoxycyclohexan-l-yl) methyl l-bromo
  • epoxycyclohexylalkyl dicarboxylates which can be employed include bis(3,4-epoxycyclohexylmethyl) pimelate and oxalate and bis(3,4- epoxy-6-methylcyclohexylmethyl) maleate, succinate, sebacate and adipate.
  • epoxycyclohexylalkyl phenylenedicarboxylates which can be employed include bis(3,4- epoxycyclohexylmethyl) terephthalate and bis(3,4- epoxy--methylcyclohexylmethyl) terephthalate.
  • Illustrative cycloaliphatic triepoxides which can be I employed include tris(3,4-epoxycyclohexanecarboxylate) of I,l,l-trimethylol propane; and tris(3,4-epoxycyclohexanecarboxylate) of 1,2,3-propanetriol.
  • the sizing composition can be applied to the fiber in a suitable solvent to control the amount of size coated onto the fiber. However, the sizing composition can be applied directly, if desired.
  • the concentration of the size in the solvent is usually in the range of from about 0.1 to about 10.0% by weight based on the total weight of the solution and is preferably from about 0.5 to about 2.0%.
  • suitable solvents are polar solvents such as the halogenated hydrocarbons, for example, methylene chloride and ethylene dichloride; diacetone alcohol, ketones and esters.
  • the sizing composition may also contain a lubricant.
  • the lubricant serves to permit more even distribution of .the size on the fiber and aids in more effective wetting of the fiber.
  • Preferred lubricants are fatty acids, amides and esters.
  • Other additives, such as coupling agents can also be added to the size solution.
  • the sizing compositions can be applied to the fibers by known methods, for example, by drawing the fibers through a bath containing the size or by spraying the size onto the fibers.
  • the drawing illustrates a preferred arrangement for sizing carbon fibers. 1n the drawing, a carbon fiber strand 2 is drawn from supply reel 4 and passed into a tube 6. The arrows indicate the direction the carbon fiber strand 2 travels.
  • the tube 6 is heated by hot air forced through the inlet tube 8 from a suitable source, such as an electric heat gun. The temperature of the hot air is sufficient to heat the tube to above the evaporation temperature of the solvent.
  • the fiber is passed along the tube and down through an opening 9 inthe bottom of the tube 6 and into the sizing bath 10.
  • the fiber- is directed down into the bath 10, through the bath and back through opening 9 into heated tube 6 by guide rollers 12, 14 and 16.
  • the fiber is passed through the heated tube to evaporate the solvent and wound on a conventional take-up roll 18.
  • the amount of size coated onto the fiber is from about-0.4 to about 5.0%, by weight based on the weight of the fiber, preferably from about 0.9 to about 1.6%.
  • the amount of size on the fiber is determined by weighing a given length of sized fiber, then dissolving the size from the fiber using a solvent for the size, drying the fiber and then reweighing the unsized fiber. From the difference in the weights the percentage of size on the fiber, based on the weight of the fiber, is calculated.
  • Carbon fibers sized with the epoxy compound sizing compositions of this invention can be used to prepare fiber reinforced composite structures. Any of the known methods for preparing such composites can be employed. For example, carbon fibers can be used to prepare filament wound composites. The epoxy sizing compositions of this invention protect the fibers from abrasion during the filament winding process. The sizing of the fiber also permits a smoother delivery of the carbon fiber during. the filament winding. In another common method, the reinforced composite structure can be prepared by incorporating chopped sized carbon fibers into the matrix resin and then forming the composite structure, for example, by press molding.
  • the sizing compositions of this invention are based on epoxide compounds, carbon fibers sized therewith are compatible with and do not interfere with adhesion between the carbon fibers and the epoxy resin-hardener systems used as the matrix resin of the composite. This is especially true when both the size composition and the matrix resin are both based on diglycidyl ethers of bisphenol A.
  • EXAMPLES l-9 Commercially available surface treated graphite fiber was sized with epoxy compounds in accordance with this invention in a suitable application process.
  • the particular size and application solvent used in each example are shown in Table 1.
  • the fiber was sized by drawing the fiber through a heated tube and sizing bath as shown in the drawing. The fiber was pulled through the size solution at a rate of 2-4 feet per minute.
  • the take-up was a typical Leesona take-up driver with a motor.
  • the size produced on the fiber ranged from soft to hard, as determined by the hand or feel of the resulting sized fiber.
  • the term soft is used to describe a sized fiber which retains its limp hand and the term hard applies to a sized fiber having a stiff hand.
  • Compound B Compound A diglycidyl ether of bisphenol A
  • Compound B diglycidyl ether of bisphenol A having a molecular weight
  • Compound C The amide of pelargonic acid.
  • Mixture E a mixture of 35% by wt. of bis-2,3-epoxycyclopentyl ether and 65% by wt. of the diglycidyl ether of bisphenol A; commercially available as ERLA 2256 from Union Carbide Corp.
  • Ex. 1 1.6 14,100 12,100 4 hours at 175C.
  • Ex. 2 1.0 13,000 Ex. 3 1.0 13,900 EX. 4 1.6 12,800 EX. 5 1.0 12,100 11,100 Ex. 6 0.9 11,900 Ex. 8 1.4 13,100 3 2 hours at 125C.
  • a matrix resin-hardener system comprising 100 EXAMPLE 1 1 parts by weight of a mixture of by weight of bis- 2,3-epoxycyclopentyl ether and 65% by weight of the diglycidyl ether of bisphenol A (see footnote E of Table l) and 29 parts by weight of a hardener comprising a eutectic mixture of metaphenylene diamine and methylene dianiline.
  • a matrix resin-hardener system comprising 100 parts by weight of N,N,N-tris(epoxypropyl)-p,p'- diaminophenyl methane and 49 parts by weight of the hardener 4,4-diaminodiphenyl sulfone.
  • the composite specimens were made in the form of an NOL ring containing about 60% by volume of sized carbon fiber.
  • the carbon fiber is passed through the epoxy resin system, through a tensioning device and onto a rotating mold. The whole system is enclosed in a vacuum chamber to provide a low void composite specimen.
  • the mold is removed from the NOL winding device and placed in a curing oven to cure the resin.
  • the time and temperature of curing each of the resin matrix-hardener systems is shown in Table 2.
  • a discussion of NOL ring specimens and their manufacture may be found in PlasticsTechnology, November 1958, pp. 1017-1024, and
  • Carbon fibers sized with soft, medium soft, and hard sizes as described in Example 1-9 were tested for abra sion resistance.
  • a typical filament winding delivery system was set up to assess the effect on size on the abrasion resistance of carbon fiber during filament winding.
  • the system consisted of a CTC Tensioner, commercially available from Compensating Tension Controls, Inc., set at 3 pounds tension.
  • the fiber was taken over an aluminum wheel, a carbon wheel, and onto a 2.6 inch diameter mandrel on a filament winding machine.
  • the degree of abrasion was measured by percent retention of original carbon fiber tensile strength.
  • the results, shown in Table 3, show the improvement in abrasion resistance of carbon fibers when sized with the epoxy size compositions.
  • compositions of this invention are selected from the group oonsisting of (a) a liquid diglycidyl ether of bisphenol A having a molecular weight of about 340 to about 380; (b) a mixture of a solid diglycidyl ether of bisphenol A having a molecular weight of about 380 to 1400 and a liquid diglycidyl ether of bisphenol A having a molecular weight of about 340 to about 380; (c) a mixture of bis-2,3-epoxycyclopentyl ether and the diglycidyl ether of bisphenol A; and (d) 2,6-diglycidyl phenyl glycidyl ether.
  • the application of the different sizing compositions produce a different feel or hand on the fiber ranging from soft to hard.
  • a soft size is obtained when the fiber is treated with 2,6-diglycidyl phenyl glycidyl ether, the diglycidyl ether of bisphenol A having a molecular weight in the range of 340 to about 380 or a eutectic mixture of 35% by weight of bis-2,3-epoxycyclopentyl ether and 65% by weight of the diglycidyl ether of bisphenol A.
  • a hard size is obtained when the fiber is treated with a mixture of about 50 to about 80% by weight, preferably 76% by weight of the solid diglycidyl ether of bisphenol A having a molecular weight of about 380 to about i400 and from about 20 to about 50% by weight, preferably 24% by weight of the liquid diglycidyl ether bisphenol A having a molecular weight in the range of about 340 to about 380.
  • a medium soft size is obtained when the carbon fiber is treated with a mixture of about 20 to about 50% by weight, preferably 37.5% by weight of the solid diglycidyl ether of bisphenol A having a molecular weight of about 380 to 1400 and about 50 to about 80% by weight, preferably 62.5% by weight of the liquid diglycidyl ether of bisphenol A having a molecular weight in the range of about 340 to 380.
  • a carbon fiber having coated on the surface thereof from about 0.4 to about 5.0% by weight, based on the weight of the fiber of a sizing composition selected from the group consisting of polyglycidyl ethers, cycloaliphatic polyepoxides and mixtures thereof.
  • a carbon fiber as set forth in claim 1 wherein the sizing composition is selected from the group consisting of:
  • a carbon fiber as set forth in claim 1 wherein the sizing composition comprises a mixture of about 50 to about by weight of a solid diglycidyl ether of bisphenol A having a molecular weight of about 380 to about 1400 and about 20 to about 50% by weight of a liquid diglycidyl ether of bisphenol A having a molecular weight of about 340 to about 380.
  • a carbon fiber as set forth in claim 1 wherein the sizing composition comprises a mixture of about 20 to about 50% by weight of a solid diglycidyl ether of bisphenol A having a molecular weight of about 380 to about 1400 and about 50 to about 80% by weight of a liquid diglycidyl ether of bisphenol A having a molecular weight of about 340 to about 380.

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  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Reinforced Plastic Materials (AREA)
  • Epoxy Resins (AREA)
US402493A 1973-10-01 1973-10-01 Sized carbon fibers Expired - Lifetime US3914504A (en)

Priority Applications (9)

Application Number Priority Date Filing Date Title
US402493A US3914504A (en) 1973-10-01 1973-10-01 Sized carbon fibers
CA208,181A CA1033232A (en) 1973-10-01 1974-08-30 Sized carbon fibers
JP10126374A JPS5715229B2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1973-10-01 1974-09-03
DE19742446097 DE2446097A1 (de) 1973-10-01 1974-09-26 Kohlefaeden mit aufgetragenen schlichtemassen
IT27908/74A IT1022474B (it) 1973-10-01 1974-09-30 Fibre di careone imbozzimate
GB4235574A GB1454424A (en) 1973-10-01 1974-09-30 Sized carbon fibres
FR7433424A FR2246663B1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1973-10-01 1974-09-30
US05/554,998 US3957716A (en) 1973-10-01 1975-03-03 Sized carbon fibers
MY1977237A MY7700237A (en) 1973-10-01 1977-12-31 Composite films

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JP (1) JPS5715229B2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
CA (1) CA1033232A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
DE (1) DE2446097A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
FR (1) FR2246663B1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
GB (1) GB1454424A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
IT (1) IT1022474B (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)
MY (1) MY7700237A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html)

Cited By (25)

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US4044540A (en) * 1976-03-04 1977-08-30 Toray Industries, Inc. Elastomer coated carbon filament reinforcing yarn or cord, method and article
US4145472A (en) * 1977-09-06 1979-03-20 Hitco Fibrous carbonaceous material sized with a glycidylhydantoin sizing
US4216262A (en) * 1979-05-23 1980-08-05 Great Lakes Carbon Corporation Surface treatment of carbon fibers
US4220686A (en) * 1975-03-12 1980-09-02 Desoto, Inc. Encapsulated impregnated rovings
US4269876A (en) * 1977-10-04 1981-05-26 Rolls-Royce Limited Treatment of carbon fibre
EP0045574A1 (en) * 1980-07-14 1982-02-10 Celanese Corporation Sized carbon fibers and thermoplastic polyester based composite structures employing the same
FR2512474A1 (fr) * 1981-09-07 1983-03-11 Toho Beslon Co Agent d'encollage du type emulsion pour fibres de carbone, procede de preparation et methode d'utilisation de celui-ci
US4394467A (en) * 1981-06-22 1983-07-19 Celanese Corporation Sized carbon fibers capable of use with polyimide matrix
US4443566A (en) * 1983-04-25 1984-04-17 Celanese Corporation Sized reinforcing fibers suitable for use in composites of improved impact resistance
US4446255A (en) * 1982-12-29 1984-05-01 Celanese Corporation Sized carbon fibers suitable for use in composites of improved impact resistance
US4526940A (en) * 1982-06-07 1985-07-02 Ciba-Geigy Corporation Hydroxyl terminated polyfunctional epoxy curing agents
US4531354A (en) * 1980-05-22 1985-07-30 Desoto, Inc. Thermally curable wet-impregnated rovings
US4555446A (en) * 1982-07-05 1985-11-26 Toray Industries, Incorporated Carbon fiber and process for preparing same
US4654264A (en) * 1984-05-16 1987-03-31 Mitsubishi Rayon Co., Ltd. Method of sizing carbon fiber and a carbon fiber composition
US4861855A (en) * 1987-03-31 1989-08-29 Amoco Corporation Polyamide-imide compositions from bisphenoxyphenyl diamine tricarboxylic anhydride and tetracarboxylic dianhydride
US4940740A (en) * 1989-04-21 1990-07-10 Basf Aktiengesellschaft Single phase toughened heat-curable resin systems exhibiting high strength after impact
US4981942A (en) * 1987-03-31 1991-01-01 Amoco Corporation Polyamide-imide composition based on bisphenoxyphenyl diamines
US5227238A (en) * 1988-11-10 1993-07-13 Toho Rayon Co., Ltd. Carbon fiber chopped strands and method of production thereof
US5229202A (en) * 1990-05-22 1993-07-20 Mitsubishi Kasei Corporation Carbon fiber and carbon fiber-reinforced resin composition using it
WO1995026433A1 (en) * 1994-03-28 1995-10-05 Bp Chemicals (Hitco) Inc. Process for the preparation of flexible carbon yarn and carbon products made therefrom
US5462799A (en) * 1993-08-25 1995-10-31 Toray Industries, Inc. Carbon fibers and process for preparing same
US20090092831A1 (en) * 2006-04-28 2009-04-09 Toho Tenax Europe Gmbh Carbon Fiber
US8309644B1 (en) * 2011-08-29 2012-11-13 GM Global Technology Operations LLC Methods of treating carbon fibers, fiber-reinforced resins, and methods of making the fiber-reinforced resins
US9757768B2 (en) 2013-12-23 2017-09-12 Cytec Industries Inc. Method for manufacturing sized carbon fibers for composite applications
EP4101894A1 (en) 2021-06-08 2022-12-14 SHPP Global Technologies B.V. Thermoplastic compositions and shaped articles thereof

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5665044A (en) * 1979-10-31 1981-06-02 Dainippon Ink & Chem Inc Carbon fiber-reinforced resin composition
DE3024608A1 (de) * 1980-06-28 1982-01-28 Basf Ag, 6700 Ludwigshafen Formmassen aus kohlenstoffasern und polyolefinen
JPS57171767A (en) * 1981-04-13 1982-10-22 Mitsubishi Rayon Co Sizining treatment
JP2830051B2 (ja) * 1989-05-18 1998-12-02 東レ株式会社 炭素繊維強化金属複合材料用プリフォームの製造方法
TW591157B (en) 2001-05-25 2004-06-11 Mitsubishi Rayon Co Sizing agent for carbon fiber, its water dispersing solution, carbon fiber with sizing handling, sheet matter with using the carbon fiber and carbon fiber reinforced composite
TWI220147B (en) * 2001-07-24 2004-08-11 Mitsubishi Rayon Co Sizing agent for carbon fibers and water dispersion thereof, sized carbon fibers, sheet-like articles using said carbon fibers, and carbon fiber enhanced composite material
KR101557568B1 (ko) 2011-08-22 2015-10-05 미쯔비시 레이온 가부시끼가이샤 탄소섬유용 사이징제, 그의 수분산액, 사이징제가 부착된 탄소섬유속, 시트상물, 및 탄소섬유 강화 복합재
CN107043454B (zh) 2012-05-16 2019-08-20 株式会社大赛璐 环氧基-胺加成物、树脂组合物、上胶剂、涂布有上胶剂的碳纤维及纤维强化复合材料
KR102193671B1 (ko) 2019-03-19 2020-12-21 한국과학기술연구원 벤젠 고리를 가지는 화합물로 코팅된 탄소섬유의 급속 플라즈마 처리를 통한 표면 처리 방법 및 장치, 이에 따른 탄소 섬유의 물성 향상 방법 및 물성이 향상된 탄소 섬유
TW202511401A (zh) * 2023-09-13 2025-03-16 達興材料股份有限公司 固化組成物、固化物及其應用

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US8309644B1 (en) * 2011-08-29 2012-11-13 GM Global Technology Operations LLC Methods of treating carbon fibers, fiber-reinforced resins, and methods of making the fiber-reinforced resins
CN102965928A (zh) * 2011-08-29 2013-03-13 通用汽车环球科技运作有限责任公司 处理碳纤维的方法、纤维增强树脂和制造纤维增强树脂的方法
CN102965928B (zh) * 2011-08-29 2015-11-25 通用汽车环球科技运作有限责任公司 处理碳纤维的方法、纤维增强树脂和制造纤维增强树脂的方法
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EP4101894A1 (en) 2021-06-08 2022-12-14 SHPP Global Technologies B.V. Thermoplastic compositions and shaped articles thereof

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CA1033232A (en) 1978-06-20
JPS5715229B2 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1982-03-29
JPS5059589A (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1975-05-22
FR2246663B1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1978-10-13
MY7700237A (en) 1977-12-31
DE2446097A1 (de) 1975-04-03
GB1454424A (en) 1976-11-03
FR2246663A1 (GUID-C5D7CC26-194C-43D0-91A1-9AE8C70A9BFF.html) 1975-05-02
IT1022474B (it) 1978-03-20

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