US3607059A - Process for the manufacture of filamentary carbon products - Google Patents

Process for the manufacture of filamentary carbon products Download PDF

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Publication number
US3607059A
US3607059A US812680A US3607059DA US3607059A US 3607059 A US3607059 A US 3607059A US 812680 A US812680 A US 812680A US 3607059D A US3607059D A US 3607059DA US 3607059 A US3607059 A US 3607059A
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United States
Prior art keywords
tension
oxidation
filamentary material
temperature
carried out
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Expired - Lifetime
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US812680A
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English (en)
Inventor
Louis A Joo
Frank E Snodgrass
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Akzo NV
Original Assignee
Great Lakes Carbon Corp
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Publication of US3607059A publication Critical patent/US3607059A/en
Assigned to MANUFACTURERS HANOVER TRUST COMPANY A NY CORP. reassignment MANUFACTURERS HANOVER TRUST COMPANY A NY CORP. SECURITY INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GREAT LAKES CARBON CORPORATION, A DE CORP
Anticipated expiration legal-status Critical
Assigned to FORTAFIL FIBERS, INC., A DE CORP. reassignment FORTAFIL FIBERS, INC., A DE CORP. RELEASED BY SECURED PARTY (SEE DOCUMENT FOR DETAILS). Assignors: MANUFACTURERS HANOVER TRUST COMPANY
Assigned to AKZO N.V., ARNHEM, THE NETHERLANDS reassignment AKZO N.V., ARNHEM, THE NETHERLANDS ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: GREAT LAKES CARBON CORPORATION
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
    • D01F9/225—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles from stabilised polyacrylonitriles
    • 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
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
    • D01F9/21—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F9/22—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products from macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from polyacrylonitriles
    • 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
    • D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
    • D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
    • D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
    • D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
    • D01F9/32—Apparatus therefor
    • 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
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S264/00—Plastic and nonmetallic article shaping or treating: processes
    • Y10S264/19—Inorganic fiber

Definitions

  • ABSTRACT Process for the manufacture of carbon and grall!- 1r phit fil m nt odu t from olyacrylonitrile filamentary [50] Field of Search 23/2091, material wherein said fil t material is Subjected to a 209-41 8/1 preliminary tension-free noncombustive partial oxidation and 56 R f Cted thereafter stretched to introduce or restore orientation in the l l e fences l polymer strands prior to being oxidized under tension fol- UNITED STATES PATENTS lowed by carbonization in a nonoxidizing atmosphere at a 3,533,743 10/1970 Prescott et a1. 23/209.1 temperature of at least 700C.
  • An object of this invention therefore is to provide a method which will allow the continuous oxidation under tension of acrylic filamentary material which cannot presently be so treated. Another object is to increase the supply of acrylic filamentary material that can be successfully converted to carbon and graphite without losing its filamentary structure.
  • the material is first stretched at about 100 C., for instance in hot water or steam. It isthen oxidized under tension, usually in air, at a temperature within the range of about 200 to 250 C. for an effective period of about 1 to 2 hours. This is followed by a batch oxidation in a flowing oxidizing atmosphere at similar temperatures for a period of about 5 to hours. This batch oxidation is performed on fibers that are free from mechanical tension. The oxidized fibers are then graphitized at high temperature in a nonoxidizing atmosphere. If nongraphitic carbon fibers are desired, the postoxidative treatment of the fibers may be stopped at temperatures as low as 700 C.
  • the unstretched yarn is first subjected to a partial oxidation without tension followed by a stretching operation before the conventional single or two-stage oxidation and the graphitization operations are performed.
  • the preliminary oxidation process of this improvement is carried out in air at a temperature of about 200250 C. for about I to about 8 hours; the stretching step is carried out in a boiling water environment.
  • the partially oxidized filament is stretched up to about 200 percent of its original length. This improvement is illustrated by the path which follows line A of the flowsheet.
  • improvement B the yarn is first stretched according to the basic process of the art, up to about percent of its original length, but the single or two-stage oxidation and the graphitization step are preceded by an oxidation without significant tension followed by a restretching of the yarn, up to about 200 percent of its original length.
  • the path which goes through line B in the drawing schematizes this approach.
  • EXAMPLE 1 (R)Registercd trademark PAN staple yarn was stretched in boiling water to 210 percent ofits original length. It was then passed through a conventional continuous oxidation unit on a pair ofdrivcn grooved rolls. After an effective residence time of l hour in air at 230 C.. the yarn was fused and unfit for further processing.
  • EXAMPLE 1 l Unstretched Orion staple acrylic yarn was preoxidized in skein form for 4 hours at 220 C. and subsequently stretched in boiling water to 200 percent of its original length. It was then processed as in example 2 to a graphitized product poscombustive oxidation process carried out under mechanical tension and (b) to a carbonization stage in a nonoxidizing atmosphere at a temperature of at least 700 C., the improvet whish snsi ts n first j c ing thefl amc y material to a preliminary substantially tension-free noncombustive partial oxidation in air at a temperature within the range of about 200250 C. for a duration within the range of about 1 to 8 hours followed by stretching of the partially oxidized filamentary material by up to about 200 percent of its original length in a boiling water environment.
  • a process for the manufacture of carbon and graphite filament and yarn which comprises subjecting a precursor polyacrylonitrile filamentary material (a) to a noncombustive i oxidation process consisting of a continuous phase carried out i under tension and a secondary batch phase carried out ⁇ without tension, and (b) to a carbonization stage in a nonox- E idizing atmosphere at a temperature of at least 700 C., the improvement which consists in first subjecting the filamentary material to a preliminary substantially tension-free noncombustive partial oxidation in air at a temperature within the range of about 200-250 C. for a duration within the range of about 1 to 8 hours followed by stretching of the partially oxidized filamentary material by up to about 200 percent of its original length in a boiling water environment.
  • Example 1 Orlon PAN staple yarn was stretched in boiling water to 210% of its original length. It was then passed through a conventional continuous oxidation unit on a pair of driven grooved rolls. After an effective residence time of one hour in air at 230C., the yarn was fused and unfit for further processing.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Fibers (AREA)
  • Carbon And Carbon Compounds (AREA)
US812680A 1969-04-02 1969-04-02 Process for the manufacture of filamentary carbon products Expired - Lifetime US3607059A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US81268069A 1969-04-02 1969-04-02

Publications (1)

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US3607059A true US3607059A (en) 1971-09-21

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US812680A Expired - Lifetime US3607059A (en) 1969-04-02 1969-04-02 Process for the manufacture of filamentary carbon products

Country Status (4)

Country Link
US (1) US3607059A (de)
JP (1) JPS4812090B1 (de)
DE (1) DE2015820C3 (de)
GB (1) GB1284142A (de)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3841079A (en) * 1970-04-14 1974-10-15 Celanese Corp Carbon filaments capable of substantial crack diversion during fracture
US3914960A (en) * 1971-04-13 1975-10-28 Hitco Apparatus for continuously producing preoxidized textile products
US4256607A (en) * 1976-10-05 1981-03-17 Toho Beslon Co., Ltd. Process for production of activated carbon fibers
US4285831A (en) * 1976-10-05 1981-08-25 Toho Beslon Co., Ltd. Process for production of activated carbon fibers
US4856179A (en) * 1983-04-21 1989-08-15 Hoechst Celanese Corp. Method of making an electrical device made of partially pyrolyzed polymer
US4938941A (en) * 1985-10-11 1990-07-03 Basf Aktiengesellschaft Partially carbonized polymeric fibrous material having an electrical resistivity of enhanced stability
US10407802B2 (en) 2015-12-31 2019-09-10 Ut-Battelle Llc Method of producing carbon fibers from multipurpose commercial fibers

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3285696A (en) * 1960-08-25 1966-11-15 Tokai Denkyoku Seizo Kabushiki Method for the preparation of flexible carbon fibre
US3412062A (en) * 1964-04-24 1968-11-19 Nat Res Dev Production of carbon fibres and compositions containing said fibres
US3533743A (en) * 1968-05-28 1970-10-13 Great Lakes Carbon Corp Process for the manufacture of continuous high modulus carbon yarns and monofilaments
US3552923A (en) * 1966-06-28 1971-01-05 William George David Carpenter Production of carbon fibers

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3285696A (en) * 1960-08-25 1966-11-15 Tokai Denkyoku Seizo Kabushiki Method for the preparation of flexible carbon fibre
US3412062A (en) * 1964-04-24 1968-11-19 Nat Res Dev Production of carbon fibres and compositions containing said fibres
US3552923A (en) * 1966-06-28 1971-01-05 William George David Carpenter Production of carbon fibers
US3533743A (en) * 1968-05-28 1970-10-13 Great Lakes Carbon Corp Process for the manufacture of continuous high modulus carbon yarns and monofilaments

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Vosburgh Textile Research Journal Vol. 30, 1960, pages 882 896 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3841079A (en) * 1970-04-14 1974-10-15 Celanese Corp Carbon filaments capable of substantial crack diversion during fracture
US3914960A (en) * 1971-04-13 1975-10-28 Hitco Apparatus for continuously producing preoxidized textile products
US4256607A (en) * 1976-10-05 1981-03-17 Toho Beslon Co., Ltd. Process for production of activated carbon fibers
US4285831A (en) * 1976-10-05 1981-08-25 Toho Beslon Co., Ltd. Process for production of activated carbon fibers
US4856179A (en) * 1983-04-21 1989-08-15 Hoechst Celanese Corp. Method of making an electrical device made of partially pyrolyzed polymer
US4938941A (en) * 1985-10-11 1990-07-03 Basf Aktiengesellschaft Partially carbonized polymeric fibrous material having an electrical resistivity of enhanced stability
US10407802B2 (en) 2015-12-31 2019-09-10 Ut-Battelle Llc Method of producing carbon fibers from multipurpose commercial fibers
US10961642B2 (en) 2015-12-31 2021-03-30 Ut-Battelle, Llc Method of producing carbon fibers from multipurpose commercial fibers

Also Published As

Publication number Publication date
JPS4812090B1 (de) 1973-04-18
GB1284142A (en) 1972-08-02
DE2015820B2 (de) 1972-06-08
DE2015820A1 (de) 1970-11-19
DE2015820C3 (de) 1973-01-04

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Legal Events

Date Code Title Description
AS Assignment

Owner name: MANUFACTURERS HANOVER TRUST COMPANY A NY CORP.

Free format text: SECURITY INTEREST;ASSIGNOR:GREAT LAKES CARBON CORPORATION, A DE CORP;REEL/FRAME:004376/0430

Effective date: 19850228

AS Assignment

Owner name: FORTAFIL FIBERS, INC., A DE CORP.

Free format text: RELEASED BY SECURED PARTY;ASSIGNOR:MANUFACTURERS HANOVER TRUST COMPANY;REEL/FRAME:005221/0871

Effective date: 19870724

AS Assignment

Owner name: AKZO N.V., ARNHEM, THE NETHERLANDS

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNOR:GREAT LAKES CARBON CORPORATION;REEL/FRAME:005277/0858

Effective date: 19900103