EP0329128A2 - Verfahren zur Herstellung von Kohlenstoffasern mittels Vorstreckung - Google Patents

Verfahren zur Herstellung von Kohlenstoffasern mittels Vorstreckung Download PDF

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Publication number
EP0329128A2
EP0329128A2 EP89102638A EP89102638A EP0329128A2 EP 0329128 A2 EP0329128 A2 EP 0329128A2 EP 89102638 A EP89102638 A EP 89102638A EP 89102638 A EP89102638 A EP 89102638A EP 0329128 A2 EP0329128 A2 EP 0329128A2
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EP
European Patent Office
Prior art keywords
precursor
stretching
temperature
carbon fiber
tow
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Granted
Application number
EP89102638A
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English (en)
French (fr)
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EP0329128B1 (de
EP0329128A3 (de
Inventor
James Toner Paul, Jr.
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Hexcel Corp
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Hercules LLC
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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
    • 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
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D10/00—Physical treatment of artificial filaments or the like during manufacture, i.e. during a continuous production process before the filaments have been collected
    • D01D10/02—Heat treatment
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/12—Stretch-spinning methods

Definitions

  • This invention relates to improvements in the manufacture of carbon fiber from polyacrylonitrile polymers.
  • This inven­tion more particularly, relates to producing high quality and performance carbon fiber at significant cost savings through enhancing throughputs of precursor materials used in making such carbon fiber.
  • This invention still more particularly, relates to the discovery and exploitation of a limited temperature range wherein a multitude of filaments of the polyacrylonitrile polymer, such multitude often called "carbon fiber (polyacrylonitrile) precursor" or “precursor” for short, may be safely stretched up to four or more times its original length after formation but prior to the oxida­tion used in making the carbon fiber.
  • PAN-based carbon fiber (for purposes of describing this invention hereafter called "carbon fiber") is a well-known material that is over 85% by weight elemental carbon. Such carbon fiber is notable for enabling manufacture of light weight composite materials and other articles of manufacture of exceptional tensile strength and modulus.
  • the cost of making carbon fiber under current procedures can be divided into two categories.
  • Other costs in making carbon fiber include the costs of oxidizing and then carboniz­ing the precursor, costs associated with the process control of such oxidation and carbonization and testing costs. Since only about half by weight of the precursor becomes carbon fiber, it can be seen that reduction per pound of precursor manufacturing costs results in about twice that reduction per pound in carbon fiber.
  • This invention more specifically, relates to an improve­ment in the process of manufacturing carbon fiber, the process comprising (a) forming a polyacrylonitrile polymer in a sol­vent for such polymer, (b) extruding the polymer through a die to provide a multitude of continuous filaments, (c) drawing these filaments to a longer length in making a precursor tow and (d) oxidizing and then carbonizing the precursor tow in a series of ovens and furnaces to provide the carbon fiber, the improvement comprising: (i) selecting for the polyacryloni­trile polymer a material that stretches in filamentary form as the precursor tow to a length that is at least two times its original length at a temperature in a range above about 140°C and below that temperature (e.g.
  • stretching prior to oxidation preferably consists essentially of stretch­ing in the limited temperature range preceded by stretching at temperatures below boiling water temperature. Also, such stretching prior to stretching in the limited temperature range preferably comprises stretching under circumstances that plasticize the filaments.
  • the polyacrylonitrile precursor useful in making carbon fiber in accordance with this invention comprises a polymer made by addition polymerization, either in solution or other­wise, of ethenic monomers (i.e. monomers that are ethyleni­cally unsaturated), at least about 80 mole percent of which comprise acrylonitrile.
  • the preferred polyacrylonitrile precursor polymers are copolymers of acrylonitrile and one or more other monofunctional ethenic monomers. Available ethenic monomers are diverse and include, for example, acrylates and methacrylates; unsaturated ketones; and acrylic and meth­acrylic acid, maleic acid, itaconic acid and their salts.
  • Preferred comonomers comprise acrylic or methacrylic acids or their salts, and the preferred molar amounts of the comonomer ranges between about 1.5 and 3.5%.
  • the polyacrylonitrile precursor polymers suitable for making carbon fiber hereof are soluble in organic and/or inorganic solvents such as dimethylsulfoxide, dimethyl formamide, zinc chloride or sodium thiocyanate solutions.
  • organic and/or inorganic solvents such as dimethylsulfoxide, dimethyl formamide, zinc chloride or sodium thiocyanate solutions.
  • a solution is formed from water, polyacrylonitrile polymer and sodium thiocyanate at exemplary respective weight ratios of about 60:10:30. This solution is concentrated through evaporation and filtered to provide a spinning solution.
  • the spinning solution preferably comprises about 15% by weight of the polyacrylonitrile polymer.
  • the spinning solution is passed through spinnerets using dry, dry/wet or wet spinning to form the polyacrylonitrile precursor.
  • the preferred polyacrylonitrile precursor is made using a dry/wet spinning wherein a multitude of filaments are formed from the spinning solution and pass from the spinneret through an air gap or other gap between the spinneret and a coagulant preferably comprising aqueous sodium thiocyanate. After exiting from the coagulant bath, the spun filaments are washed and then stretched again to several times their original length in hot water and steam. (See U.S.
  • the polyacryloni­trile precursor is treated with sizing agents such as silane compounds (see U.S. Patent 4,009,248 incorporated herein by reference).
  • the polyacrylonitrile precursor (preferably silane sized) is in the form of tows in bundles comprising a multi­tude of filaments (e.g. 1,000, 10,000 or more).
  • the tows or bundles may be a combination of two or more tows or bundles, each formed in a separate spinning operation.
  • FIG. 1 A thermal response curve in air of a preferred poly­acrylonitrile precursor suitable for use in making the carbon fibers of this invention is shown in Figure 1.
  • This precursor is made from a monomer composition comprising about ninety eight mole percent (98%) acrylonitrile and about two mole percent (2%) methacrylic acid.
  • the denier per filament of the polyacrylonitrile precursors desirably ranges between 0.6 and 6.0 or higher.
  • the particular denier of the polyacrylonitrile precursor chosen influences subsequent processing of the precursor into carbon fiber hereof.
  • larger denier precursor e.g. 1.33 denier per filament or above precursor is preferably stretched at temperatures below 200°C (e.g. about 150 - 160°C) to reduce its denier to less than 0.8 prior to significant oxidation. Greater stretching in the limited temperature range reduces the need for such stretching in later, e.g., during oxidation, manufacturing steps in making the carbon fiber.
  • the resultant precursor is up to 4.0 times or more its orig­inal length; and due to the minimal reaction at temperatures within this range may be in amounts selectively calculated in advance to provide the denier desired for subsequent oxidation and stabilization.
  • a 2.2 denier per filament precursor may be stretched to twice its original length to yield a 1.1 denier per filament material by a Stretch Ratio (S.R.) of 2 according to the following formula: where L o is length out, L i is length in (i.e. original length), d S is original denier and d N is new denier.
  • Desired stretch ratio (S.R.) may be achieved by drawing the precursor faster through the desired heated zone (e.g. temperature between 150°C and 160°C) that it is permitted to enter this zone.
  • FIG. 2 illustrates in schematic form the design of stretching device 20 useful in practice of this invention.
  • Device 20 of Figure 2 comprises supports 22 which carry platform 24 on which inlet roll stack 26, steam heated roll stack 28, steam heated tube 30 and outlet roll stacks 32 and 34 are mounted.
  • Steam heated tube 30 is heated by steam passing through a jacket surrounding the tube walls.
  • gas inlet tube 36 is mounted to the downstream end of steam heated tube 30 and provides for entry of heated air or other gas when countercurrent gas heating is used in heat-up of the precursor traveling between about inlet and outlet roll stacks 26, 34.
  • Control 38 monitors inlet and outlet counter-­rolls 40, 42 which can also measure tension and line speed as read out in control 38.
  • Access port 44 permits stringing precursor through steam heated roll stack 28.
  • Steam heated roll stack 28 is optionally used in provid­ing preliminary heat transfer to the precursor as it travels around the steam heated rolls 28. This preliminary heat transfer permits shorter heated lengths of steam heated tube 30, if desired.
  • inventions of the Device 20 of Figure 2 such as length of steam heated tube 30, use or non-use of steam heated roll stack 28 and gas flow velocity, direction and placement of inlet tube 36 as well as temperatures used for heating thereof are selected as a matter of design choice so as to provide rapid heat-up of the precursor as well as compatibil­ity with the oxidation and carbonization line speeds in the carbon fiber process.
  • Initial tow spacing that ranges preferably between about 2 and 4.5 tows per 2.54 centimeter for 12000 filament tows are preferred for flow of heat transfer medium, such spacing advantageously inherently increasing as stretching proceeds.
  • the polyacrylonitrile precursor after stretching in the limited temperature range according to this invention is oxidized in one or more ovens preferably maintained at temperatures between 200°C and 300°C.
  • ovens preferably maintained at temperatures between 200°C and 300°C.
  • a variety of oven geometries are known to provide appropriate oxidation in making carbon fiber and any of these ovens may be suitably employed in accordance with this invention.
  • a series of ovens or series of passes through a single oven
  • the precursor that is undergoing oxidation optionally stretched to a longer length than the length it has upon entering the oxidation oven.
  • the oxidized (and stabilized) precursor is passed to one or more furnaces for carbonization in an inert atmosphere.
  • At least two furnaces are employed respectively at temperatures between 400°C and 800°C and between 1000°C and 1400°C.
  • Still higher modulus carbon fiber is made through using still another furnace having tempera­tures above 1800°C, e.g. between 2000°C and 2800°C.
  • the fiber undergoing carbonization is desirably stretched or at least not allowed to shrink in the temperature range between 400°C and 800°C and 2000°C and 2800°C.
  • the carbonized fiber After exit from the high temperature furnace the carbonized fiber is surface treated.
  • a variety of surface treatments are known in the art.
  • Preferred surface treatment is an electrolytic surface treatment and the degree of surface treatment is ordinarily a function of the carbonization temperatures used in making the fiber.
  • the preferred electrolytic surface treatment comprises passing the fiber through a bath containing an aqueous ammonium bicarbonate or sodium hydroxide solution (e.g. 0.5 - 3% by weight). The current is applied to the fiber at between about 0.1 and 5 columbs/inch of fiber per 12,000 filaments.
  • the resulting surface treated fiber is then preferably sized with an epoxy compatible sizing agent such as Shell epoxy Epon 834.
  • Polyacrylonitrile precursors were made using an air gap wet spinning process.
  • the polymer of the precursor had an intrinsic viscosity between about 1.9 and 2.1 deciliters per gram using a concentrated sodium thiocyanate solution as the solvent.
  • the spinning solution and coagulants comprised an aqueous solution of sodium thiocyanate.
  • the polymer was made from a monomer composition that was about 98 mole % acrylo­nitrile and 2 mole % methacrylic acid.
  • the precursors were stretched so that their length in tow form was about six times greater after steam stretching compared to their length after extrusion from the spinnerets. Table A shows the character­istics of the resulting precursor which were nominal 1.3 and 0.8 dpf (denier per filament).
  • the precursors were then stretched at a temperature of 158°C with a residence time of about six (6) minutes at that temperature. After stretching, the stretched precursor was oxidized in stages generally at 234°C and then 249°C.
  • the oxidized fiber was then passed through a low temperature furnace with a non-oxidizing atmosphere (nitrogen) at a temperature between 600°C and 800°C (tar removal) and then passed to a high-temperature furnace having a temperature between 1200°C and 1400°C and a non-oxidizing atmosphere (nitrogen).
  • nitrogen non-oxidizing atmosphere
  • tar removal tar removal
  • Tables B and C show the stretch of the fiber undergoing carbonization as it passes through the tar removal (TR) and high temperature (Cl) furnaces along with the calculated dpf of the filament based on the stretch imparted at 158°C. Under each level of stretch in these tables the tensile strength and modulus properties are listed for the fiber having the calculated dpf and stretch during passage through the TR and Cl furnaces.
  • Tables B and C show results from using the 1.3 dpf precursor of Table A; Table D shows the result of using the 0.8 dpf precursor of Table A.
  • the first value in columns 4 through 9 of Table A is tensile strength of the resultant carbon fiber in psi times 1000 and the second value is modulus in psi times 1,000,000. Modulus and tensile strength measurements were made using strand and tow test (Impregnated Strand) procedures. TABLE B (1.33 dpf) TR/Cl STRETCH Run No. Calc.
  • Polyacrylonitrile precursor was made generally according to the conditions previously described except that it had no steam stretching and its denier was 1.2 dpf.
  • the 1.2 dpf polyacrylonitrile precursor fiber was stretched to twice its original length (i.e. s. r. equals 2) at a temperature of 158°C and wound around a spool and stored.
  • the precursor was then oxidized by passing it through air circulation ovens at temperatures for the times shown in the following Table D. TABLE D Temperatures Time (minutes) 158°C 2.05 240°C 17.73 245°C 14.43 248°C 17.72 250°C 17.72 250°C 4.43
  • the oxidized precursor passed from the last oxidation oven through a low temperature (tar removal) furnace. Then the partially carbonized fiber passed through a first low temperature furnace held at 1425°C and then a second high temperature furnace held at 2500°C.
  • Table F shows the properties of carbon fiber made according to the procedures of this Example. TABLE F Run Modulus a Tensile Strength b Density 135.1 58.2 606 135.2 60.1 615 135-3 61.5 628 135-4 61.4 558 a 106 psi b 103 psi
  • precursor was made under conditions generally described heretofore.
  • the precursor had a 1.67 dpf (12,000 filaments per tow) and had not been stretched under steam.
  • the precursor was passed through a device like that shown in Figure 2 and stretched four (4) times its original length (i.e. S.R. equals 4) after a residence of 0.8 minutes at about 158°C.
  • S.R. equals 4
  • the residence time was increased to 0.33 minutes at 158°C, the tows broke unacceptably after a stretch that made them 3.3 their original length.
  • the precursor had reduced cosmetics at stretch ratios (S.R.) which equaled 2.0 and 2.3 at these respective 0.25 minutes and 0.33 minutes residences at 158°C.
  • the precursor used was made from a polyacrylonitrile polymer using sodium thiocyanate as solvent and coagulant and an air gap spinning process, as described heretofore.
  • the fiber was only stretched in water and had a 2.67 dpf and 12,000 filaments per tow.
  • Methacrylic acid was used in making the polyacrylonitrile polymer.
  • the 2.67 dpf precursor was stretched in a prototype device like that shown in Figure 2, also described herein­before.
  • Hot air at 158°C was circulated in counter-current flow in tube 30 around the tows which were spaced about 1.8 toss per centimeter.
  • Steam at 71 psig was passed into the jacket of tube 30 and into the rolls of roll stack 28.
  • the line speed was gradually increased with the stretch ratio held at 3.9 (i.e. precursor was 3.9 times as long after stretching as compared to length prior to stretching).
  • Tensions of the precursor were measured in the rolls stacks 26, 34.
  • Table H shows the results of making a nominal 0.8 dpf precursor from the aforedescribed 2.67 precursor described above using the procedures of this invention.
  • TABLE H Run No. No. of Tows Band Width of Tows Output Line Speed Stretch Ratio Tension (gpd) at Pin No. 1 4 10 77 10 1.8 tows/cm 25 ft/min. 3.34X 0.344 0.323 0.321 87 10 1.8 cm 25 3.34X 0.332 0.325 0.326 Hot air at 158°C, steam tube and rolls at 72 psig, 2.67 dpf/12K precursor.
  • Control. 2 The invention. 3 "Carb.” stands for carbonization. 4 Four ovens at temperatures shown; low temperature furnace temperature between 600 and 800°C; high temperature furnace at about 1350°C. Stretch recited for carbonization is stretch across high and low temperature furnaces.
  • the tension developed at increasing temperatures and 0% stretch (i.e. constant length) for various precursors was measured.
  • the tension measured versus the temperature to which each precursor was heated at this 0% stretch is shown in Figure 3 for four polyacrylonitrile materials.
  • the monomer composition for the precursor of Curve A in Figure 3 included acrylonitrile, methacrylic acid and methylacrylate.
  • the monomer composition used in making the precursor of Curve B in Figure 3 included acrylonitrile and methacrylic acid.
  • the monomer composition used in making the precursor of Curve C included acrylonitrile, itaconic acid and methylacrylate.
  • Figure 5 shows the results of stretching different denier precursors until breaking at various temperatures.
  • the monomer composition used in making each of the precursors in Figure 5 was 98 mole % acrylonitrile and 2 mole % meth­acrylic acid.
  • Precursors D, E and F were not stretched in steam and have therefore somewhat less previous stretch imparted than precursors G and H (which were steam stretched).

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  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Fibers (AREA)
  • Artificial Filaments (AREA)
  • Yarns And Mechanical Finishing Of Yarns Or Ropes (AREA)
EP89102638A 1988-02-16 1989-02-16 Verfahren zur Herstellung von Kohlenstoffasern, oder ihren Ausgangsfasern, mittels Vorstreckung Revoked EP0329128B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US15638988A 1988-02-16 1988-02-16
US156389 1988-02-16

Publications (3)

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EP0329128A2 true EP0329128A2 (de) 1989-08-23
EP0329128A3 EP0329128A3 (de) 1991-03-13
EP0329128B1 EP0329128B1 (de) 1999-01-20

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EP89102638A Revoked EP0329128B1 (de) 1988-02-16 1989-02-16 Verfahren zur Herstellung von Kohlenstoffasern, oder ihren Ausgangsfasern, mittels Vorstreckung

Country Status (7)

Country Link
EP (1) EP0329128B1 (de)
JP (1) JP3033960B2 (de)
AT (1) ATE176012T1 (de)
CA (1) CA1327258C (de)
DE (1) DE68928911T2 (de)
ES (1) ES2128296T3 (de)
IL (1) IL89271A (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2770233A1 (fr) * 1997-10-27 1999-04-30 Messier Bugatti Procede de fabrication de preformes en fibres de carbone
EP2647745A4 (de) * 2010-11-30 2014-06-11 Toray Industries Verfahren zur herstellung einer polyacrylnitrilfaser und verfahren zur herstellung einer kohlefaser
US10407802B2 (en) 2015-12-31 2019-09-10 Ut-Battelle Llc Method of producing carbon fibers from multipurpose commercial fibers

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1324041A (en) * 1969-10-31 1973-07-18 Nippon Carbon Co Ltd Method of producing carbon fibres
DE2211639C3 (de) * 1972-03-10 1978-12-14 Bayer Ag, 5090 Leverkusen Verfahren zur Herstellung von Kohlenstoff-Fäden
JPS6039763A (ja) * 1983-08-11 1985-03-01 Japan Storage Battery Co Ltd 電解液循環装置を備える鉛蓄電池
JPS6156327A (ja) * 1984-08-28 1986-03-22 Canon Inc 表示パネルの駆動法
JPH0742605B2 (ja) * 1987-09-16 1995-05-10 日機装株式会社 アクリル系繊維の製造方法

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2770233A1 (fr) * 1997-10-27 1999-04-30 Messier Bugatti Procede de fabrication de preformes en fibres de carbone
WO1999022052A1 (fr) * 1997-10-27 1999-05-06 Messier-Bugatti Procede de fabrication de preformes en fibres de carbone
EP2647745A4 (de) * 2010-11-30 2014-06-11 Toray Industries Verfahren zur herstellung einer polyacrylnitrilfaser und verfahren zur herstellung einer kohlefaser
US8845938B2 (en) 2010-11-30 2014-09-30 Toray Industries, Inc. Polyacrylonitrile fiber manufacturing method and carbon fiber manufacturing method
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
US12146242B2 (en) 2015-12-31 2024-11-19 Ut-Battelle, Llc System for producing carbon fibers from multipurpose commercial fibers

Also Published As

Publication number Publication date
DE68928911D1 (de) 1999-03-04
CA1327258C (en) 1994-03-01
IL89271A (en) 1992-12-01
ES2128296T3 (es) 1999-05-16
IL89271A0 (en) 1989-09-10
JPH026627A (ja) 1990-01-10
JP3033960B2 (ja) 2000-04-17
EP0329128B1 (de) 1999-01-20
DE68928911T2 (de) 1999-05-27
EP0329128A3 (de) 1991-03-13
ATE176012T1 (de) 1999-02-15

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