US3720759A - Process for the production of carbon and graphite fibers - Google Patents

Process for the production of carbon and graphite fibers Download PDF

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Publication number
US3720759A
US3720759A US00039517A US3720759DA US3720759A US 3720759 A US3720759 A US 3720759A US 00039517 A US00039517 A US 00039517A US 3720759D A US3720759D A US 3720759DA US 3720759 A US3720759 A US 3720759A
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US
United States
Prior art keywords
fibers
temperature
fiber
solvent
tetrachloride
Prior art date
Legal status (The legal status 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 status listed.)
Expired - Lifetime
Application number
US00039517A
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English (en)
Inventor
D Overhoff
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sigri GmbH
Original Assignee
Sigri Elektrograhit GmbH
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Filing date
Publication date
Priority claimed from DE19702016445 external-priority patent/DE2016445C/de
Application filed by Sigri Elektrograhit GmbH filed Critical Sigri Elektrograhit GmbH
Application granted granted Critical
Publication of US3720759A publication Critical patent/US3720759A/en
Anticipated expiration legal-status Critical
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
    • 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

  • Carbon fibers are produced by treatmg synthetic polymeric fibers with a solution of a condensation Foreign Application Priority D918 agent at a temperature of 180 to 230C to effect April 7, 1970 Germany ..P 20 16 445.8 coss'linking aYd/OT cyclizatio within the Polymeric fibers and thereafter heating the treated fibers to a 52 U.S. c1 ..423/447,s/115.5 temperature between in an atmosphere [51 1111.01.
  • Titanium tetrachloride, lead tetrachloride, tin tetrachloride, and tin tetrabromide [56]
  • References Cited are used as condensation agents, preferably in the form of complexes in a solvent such as high-boiling UNITED STATES PATENTS ethers and esters.
  • Dimethylformamide is used as a 3,242,000 3/1966 Lynch ..117/46 complex formero-nitwanisele, y p 3,416,874 12/1968 Robin... ....1l7/46 X late, and iso-octadecylbenzoate are used as both so]- 3,529,934 9/1970 Shindo Vietnamese23/209.1 vent and complex former.
  • My invention relates to a method of improving the suitability of synthetic polymer fibers for carbonization.
  • a method improving the suitability for carbonization of a non-cellulosic synthetic polymer fiber in which the fiber is contacted with one or more condensation agents in order to effect cross-linking between and/or cyclization within polymer molecules, the synthetic polymer fiber then being oxidized by heating in the presence of a dehydrating agent at a temperature or temperatures withinthe range of from to 350C while free of any substantial tension.
  • the present invention is applicable to the majority of non-cellulosic synthetic polymer fibers since most fibers, if not all fibers, of this type are capable of undergoing intra-molecular cylization within and/or a certain amount of cross-linking between polymer chains leading to formation of a kind of ladder polymer.
  • the most suitable polymers for use in the method of the invention are polymers, and copolymers with suitable copolymerizable monomers, of acrylonitrile.
  • polymers and copolymers of vinylchloride, vinylesters and vinylalcohol, and 1,2-cis-polybutadiene can also be used.
  • the intramolecular and/or intra-molecular reactions which take place in the presence of the condensation agents result in the substantial retention of the molecular orientation during the subsequent heating of the fibers in an oxidizing atmosphere and later in an inert or reducing atmosphere.
  • the reaction in the presence of a condensing agent or catalyst is generally carried out at temperatures of from 180 to 230C and preferably from to 200C.
  • the cross-linking agents used are generally Lewis acids of a strength sufficient to saturate the free pairs of electrons of the polymer. While sulfur trioxide, for example, can be used as condensation catalyst, this is not a convenient material for working with on an industrial scale.
  • the preferred catalysts for use in the method according to the present invention are halides of elements of the fourth main group and sub-group of the Periodic Table. Particularly preferred condensation agents are titanium tetrachloride, lead tetrachloride, tin tetrachloride and tin tetrabromide.
  • condensation agents in the form of complexes, more especially in the form of amine complex compounds, ester complex compounds or ether complex compounds.
  • a particular advantage of the use of complexes is that the above-mentioned halide condensation agents are normally highly hydroscopic, but in the form of complex compounds, they possess a substantially grater water resistance.
  • the complexes are used in solution in suitable solvents such as high-boiling ethers and/or esters. Those solvents which are at the same time complex formers are particularly advantageous. Examples of compounds which can be used as both solvent and complex former are o-nitroanisole, di-n-butylterephthal-ate and iso-octadecylbenzoate.
  • Dimethylformamide can be used simply as complex former.
  • the solution advantageously contains at least 0.8 percent by-weight, and preferably from 1.0 to 1.5 percent by weight, of the condensation agent in the form of a complex.
  • the on-cellulosic synthetic polymer fibers used in the process of the present invention are advantageously subjected to stretching at low temperature, generally the ambient temperature, prior to being contacted with the condensation agent at an elevated temperature.
  • the stretch ratio to which the fibers are subjected is advantageously at least 1:4 and the tensile strength of the stretched fibers should be at least 4 P/den. (pond per denier).
  • This preliminary step is commonly used in the textile art and serves to align the polymer molecules.
  • Carbon and graphite fibers of high strength can be obtained from fibers pretreated in the aforespecified manner;
  • the pretreatment of synthetic polymer fibers prior to carbonization and graphitization can be carried out in a very short time.
  • the fibers can be carbonized and, if desired, graphitized in the same oven as that used in the oxidation step.
  • the temperature of the fibers is advantageously gradually raised at a rate of from 40 to 200C per hour.
  • oxidation is carried out at temperatures within the range of from 200 to 300C, the temperature of the fibers being increased at a rate of 100C per hour during oxidation.
  • the oxidation step is advantageously carried out at a temperature of from 180 to 250C and can be completed in from 1 to 5 hours.
  • the dehydrating agent used is advantageously air, although chlorine or liquid sulfur can be used for this purpose.
  • EXAMPLE 1 Fibers of a copolymer of 95 percent by weight acrylonitrile and 5 percent by weight methyl methacrylate were stretched while wet to five times their original length. The tensile strength of the stretched fibers was 4 ponds/den. The fibers were then dried at a temperature of 120C and pulled over rollers while free of any tension other than that required to pull them over the rollers, through a tank containing a 1.5 percent solution of PbCl 2 di-n-butyltere-phthalate in di-n-butylterephthalate. The bath temperature was 200C and the residence time of the fibers there was about 30 minutes.
  • the fibers were then drawn through the nip of wringer rollers and led into a second tank containing acetone in which the di-n-butylterephthalate was washed off them.
  • the fibers were then washed in a third tank containing water and dried in a tube dryer at about 120C.
  • the fibers were then subjected to an oxidation treatment. For this purpose, they were heated in a tube furnace in which the temperature control was such that a linear rise in temperature of 100C per hour was obtained in a temperature range of 200 to 300C. During the residence of the fibers in the tube furnace, a stream of air was continuously passed through the furnace.
  • the oxidized fibers were then subjected to carbonization. For this purpose, they were pulled through a second furnace to which a stream of nitrogen was continuously passed, the temperature control in the second furnace being such that there was a linear rise in temperature of about 2,000C per hour in the temperature range between 300 to 1,000C.
  • the fibers were subsequently further heated in a nitrogen atmosphere to 1,700C, the temperature control being such that a linear rise in temperature of 5,000C per minute occurred.
  • the fibers had the following mechanical properties:
  • thermoplastic polymeric fiber selected from polyacrylonitrile and polyacrylonitrile copolymers

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Inorganic Fibers (AREA)
  • Artificial Filaments (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
US00039517A 1970-04-07 1970-05-21 Process for the production of carbon and graphite fibers Expired - Lifetime US3720759A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19702016445 DE2016445C (de) 1970-04-07 Verfahren zur Herstellung von Kohlenstoff- oder Graphitfasern

Publications (1)

Publication Number Publication Date
US3720759A true US3720759A (en) 1973-03-13

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US00039517A Expired - Lifetime US3720759A (en) 1970-04-07 1970-05-21 Process for the production of carbon and graphite fibers

Country Status (10)

Country Link
US (1) US3720759A (no)
JP (1) JPS4910621B1 (no)
AT (1) AT308276B (no)
BE (1) BE755579A (no)
CH (1) CH500911A (no)
FR (1) FR2090444A5 (no)
GB (1) GB1264763A (no)
NL (1) NL141466B (no)
NO (1) NO125179B (no)
SE (1) SE367387B (no)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3903248A (en) * 1974-04-15 1975-09-02 Celanese Corp Process for the production of large denier carbon fibers
US3997638A (en) * 1974-09-18 1976-12-14 Celanese Corporation Production of metal ion containing carbon fibers useful in electron shielding applications
US4024227A (en) * 1974-11-07 1977-05-17 Japan Exlan Company Limited Process for producing carbon fibers having excellent properties
US4070446A (en) * 1973-02-01 1978-01-24 Sumitomo Chemical Company, Limited Process for production of carbon fiber
US4131644A (en) * 1974-03-29 1978-12-26 Ube Industries, Inc. Process for producing carbon fiber
WO1998031852A1 (en) * 1997-01-17 1998-07-23 Acordis Fibres (Holdings) Limited Manufacture of elongate members
US7534854B1 (en) 2005-03-29 2009-05-19 Ut-Battelle, Llc Apparatus and method for oxidation and stabilization of polymeric materials
US7649078B1 (en) 2005-03-29 2010-01-19 Ut-Battelle, Llc Apparatus and method for stabilization or oxidation of polymeric materials

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5175330U (no) * 1974-12-11 1976-06-14
JPS59187471U (ja) * 1983-05-30 1984-12-12 野間　清治 アルバム
JPS63199272U (no) * 1987-06-06 1988-12-22

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3242000A (en) * 1963-08-30 1966-03-22 Deering Milliken Res Corp Impregnated carbonized acrylic textile product and method for producing same
US3416874A (en) * 1964-02-21 1968-12-17 Crylor Production of polyacrylonitrile-based articles
US3427120A (en) * 1962-12-21 1969-02-11 Agency Ind Science Techn Producing method of carbon or carbonaceous material
US3497318A (en) * 1967-09-01 1970-02-24 Union Carbide Corp Preparation of carbon textiles from polyacrylonitrile base textiles
US3529934A (en) * 1967-01-06 1970-09-22 Nippon Carbon Co Ltd Process for the preparation of carbon fibers
US3539295A (en) * 1968-08-05 1970-11-10 Celanese Corp Thermal stabilization and carbonization of acrylic fibrous materials
US3547584A (en) * 1967-12-18 1970-12-15 Celanese Corp Graphitization of fibrous polyamide resinous materials
US3592595A (en) * 1968-11-21 1971-07-13 Celanese Corp Stabilization and carbonization of acrylic fibrous material

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3427120A (en) * 1962-12-21 1969-02-11 Agency Ind Science Techn Producing method of carbon or carbonaceous material
US3242000A (en) * 1963-08-30 1966-03-22 Deering Milliken Res Corp Impregnated carbonized acrylic textile product and method for producing same
US3416874A (en) * 1964-02-21 1968-12-17 Crylor Production of polyacrylonitrile-based articles
US3529934A (en) * 1967-01-06 1970-09-22 Nippon Carbon Co Ltd Process for the preparation of carbon fibers
US3497318A (en) * 1967-09-01 1970-02-24 Union Carbide Corp Preparation of carbon textiles from polyacrylonitrile base textiles
US3547584A (en) * 1967-12-18 1970-12-15 Celanese Corp Graphitization of fibrous polyamide resinous materials
US3539295A (en) * 1968-08-05 1970-11-10 Celanese Corp Thermal stabilization and carbonization of acrylic fibrous materials
US3592595A (en) * 1968-11-21 1971-07-13 Celanese Corp Stabilization and carbonization of acrylic fibrous material

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4070446A (en) * 1973-02-01 1978-01-24 Sumitomo Chemical Company, Limited Process for production of carbon fiber
US4131644A (en) * 1974-03-29 1978-12-26 Ube Industries, Inc. Process for producing carbon fiber
US3903248A (en) * 1974-04-15 1975-09-02 Celanese Corp Process for the production of large denier carbon fibers
US3997638A (en) * 1974-09-18 1976-12-14 Celanese Corporation Production of metal ion containing carbon fibers useful in electron shielding applications
US4024227A (en) * 1974-11-07 1977-05-17 Japan Exlan Company Limited Process for producing carbon fibers having excellent properties
WO1998031852A1 (en) * 1997-01-17 1998-07-23 Acordis Fibres (Holdings) Limited Manufacture of elongate members
US7534854B1 (en) 2005-03-29 2009-05-19 Ut-Battelle, Llc Apparatus and method for oxidation and stabilization of polymeric materials
US20090263295A1 (en) * 2005-03-29 2009-10-22 Ut-Battelle, Llc Apparatus and method for oxidation and stabilization of polymeric materials
US7649078B1 (en) 2005-03-29 2010-01-19 Ut-Battelle, Llc Apparatus and method for stabilization or oxidation of polymeric materials
US7786253B2 (en) 2005-03-29 2010-08-31 Ut-Battelle, Llc Apparatus and method for oxidation and stabilization of polymeric materials

Also Published As

Publication number Publication date
SE367387B (no) 1974-05-27
NL141466B (nl) 1974-03-15
DE2016445A1 (de) 1971-12-09
BE755579A (fr) 1971-03-01
AT308276B (de) 1973-06-25
NL7009900A (no) 1971-10-11
DE2016445B2 (de) 1972-08-17
FR2090444A5 (no) 1972-01-14
CH500911A (de) 1970-12-31
GB1264763A (en) 1972-02-23
JPS4910621B1 (no) 1974-03-12
NO125179B (no) 1972-07-31

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