US3607059A - Process for the manufacture of filamentary carbon products - Google Patents
Process for the manufacture of filamentary carbon products Download PDFInfo
- 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
- Authority
- US
- United States
- Prior art keywords
- tension
- oxidation
- filamentary material
- temperature
- carried out
- 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
Links
- 238000000034 method Methods 0.000 title claims abstract description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 13
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 230000003647 oxidation Effects 0.000 claims abstract description 33
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 33
- 239000000463 material Substances 0.000 claims abstract description 23
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 8
- 239000010439 graphite Substances 0.000 claims abstract description 8
- 238000003763 carbonization Methods 0.000 claims abstract description 7
- 229920002239 polyacrylonitrile Polymers 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 7
- 239000002243 precursor Substances 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 abstract description 4
- 239000000835 fiber Substances 0.000 description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000005087 graphitization Methods 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 229920006397 acrylic thermoplastic Polymers 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 2
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 229920002972 Acrylic fiber Polymers 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Images
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.
Landscapes
- 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)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US81268069A | 1969-04-02 | 1969-04-02 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3607059A true US3607059A (en) | 1971-09-21 |
Family
ID=25210321
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
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 (ja) |
JP (1) | JPS4812090B1 (ja) |
DE (1) | DE2015820C3 (ja) |
GB (1) | GB1284142A (ja) |
Cited By (7)
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)
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 |
-
1969
- 1969-04-02 US US812680A patent/US3607059A/en not_active Expired - Lifetime
-
1970
- 1970-03-26 GB GB04809/70A patent/GB1284142A/en not_active Expired
- 1970-04-02 DE DE2015820A patent/DE2015820C3/de not_active Expired
- 1970-04-02 JP JP45027481A patent/JPS4812090B1/ja active Pending
Patent Citations (4)
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)
Title |
---|
Vosburgh Textile Research Journal Vol. 30, 1960, pages 882 896 * |
Cited By (8)
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 |
---|---|
DE2015820B2 (de) | 1972-06-08 |
GB1284142A (en) | 1972-08-02 |
DE2015820A1 (de) | 1970-11-19 |
JPS4812090B1 (ja) | 1973-04-18 |
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 |