US3769390A - Process for producing carbon fibres - Google Patents

Process for producing carbon fibres Download PDF

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Publication number
US3769390A
US3769390A US00123368A US3769390DA US3769390A US 3769390 A US3769390 A US 3769390A US 00123368 A US00123368 A US 00123368A US 3769390D A US3769390D A US 3769390DA US 3769390 A US3769390 A US 3769390A
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Prior art keywords
fibres
furnace
carbonisation
liquid
fibre
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US00123368A
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English (en)
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R Weisbeck
G Pampus
C Suling
L Prets
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Bayer AG
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Bayer AG
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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
    • 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

Definitions

  • Carbon fibres are produced by heat-treating polyacrylonitrile fibres in an oxidizing atmosphere at a temperature between 150 C. to 400 C. followed by carbonising at a temperature of over 400 C. in a carbonising atmosphere containing 0.5-20% by volume water vapour.
  • water vapour is provided to the carbonising atmosphere by passing the fibrous material through water or a liquid containing water between the oxidative heat treatment and the carbonisation.
  • the invention relates to a process for producing thin carbon fibres, such as for use as individual filaments, fibres, yarns, woven fabrics, knitted fabrics or fleeces with thin carbon fibres by etching away during the carbonisation process, with the etching away of the fibres taking place uniformly, so that the cross-section of the fibres is appropriately reduced.
  • the heat treatment is carried out in air.
  • a tensile stress is applied to the fibres during the heat treatment.
  • the carbonisation is preferably carried out in flowing hydrogen, at times also in flowing inert gas or in a flowing gas mixture consisting of hydrogen and inert gases.
  • the temperature is in general increased by less than 300 C./ hour, up to the region of 1000 C. In some cases, the temperature is raised to between about 1500 and 1600" C.
  • the carbonisation can be followed, in a third step, by a graphitisation at temperatures of up to- 3000 C., in inert gases.
  • the two steps heat treatment and carbonisation are in most cases carried out in two separate temperature stages or heating zones. This is standard in continuous processes.
  • the finest-gauge spun fibres which can at the present time be manufactured on an industrial scale from acrylonitrile polymers have a gauge of about 1.5 dtex (decitex which is g./ 10,000 m.). This corresponds, for circular fibres, to a diameter of about 13 ,u.m. It has been found that fine-gauge polyacrylonitrile fibres are particularly suitable for the manufacture of carbon fibres. The danger of fibres fracturing when handling such materials is relatively great, especially if it is a matter of handling strips consisting of several thousand individual filaments. It is known that during the heat treatment in an oxygen-containing atmosphere and during the carbonisation a shrinkage of the fibres occurs, which amounts to a reduction in the fibre diameter of a total of about 30 to 50%.
  • Carbon fibres can for practical purposes no longer be stretched. An elongation of 2% leads, in almost all cases, to the fibre tearing. Thus, practically no reduction in the fibre diameter is achievable by stretching the carbon fibre.
  • very thin carbon fibres for example for the manufacture of carbon fibre-reinforced plastics, wherein the effectiveness of the reinforcing fibres increases with the ratio of length to diameter.
  • Thin fibres are also particularly suitable for the manufacture of fibre materials for high temperature insulations in the form of carbon fleeces and random fibre waddings.
  • the present invention was based on the task of discovering a process for the manufacture of thin carbon fibres by etching thicker fibres away as uniformly as possible.
  • a process for the manufacture of fibre products with thin carbon fibres which starts from polyacrylonitrile fibres which are converted to carbon fibres in two steps, wherein, in the first step, a heat treatment in an oxygen-containing atmosphere at between and 400 C. takes place and in the second step the carbonisation takes place at temperatures at over 400 C., and the etching away during the carbonisation is carried out in a moving atmosphere containing water vapour, the amount of water vapour being 0.5 to 20% by volume of the moving atmosphere.
  • a preferred embodiment of the process according to the invention consists of the Water vapour concentration of the flowing atmosphere during the carbonisation being established by transporting the fibres, after the heat treatment and before the carbonisation, through a liquid which consists of water or contains water.
  • a further advantage of the process according to the invention resides in that the manufacture of thin carbon fibres by etching away can be carried out continuously.
  • the procedure followed is advantageously that after the heat treatment and before the carbonisation the fibres are continuously drawn through a liquid which consists of water or contains water.
  • the liquid is then so arranged that it provides a gas-tight barrier at the inlet of the fibres into the carbonisation furnace.
  • the process is carried out by, for example, drawing a ribbon of endless fibres of acrylonitrile polymers through a furnace in which a heat treatment in air lasting some hours, at temperatures between about 200 and 400 C., is carried out under tension. From this furnace, the heattreated fibres are then drawn into the carbonisation furnace, which is for example a tubular furnace. In this furnace, a temperature distribution which rises strictly continuously is maintained along the tube axis between the inlet and outlet, so that during their passage through this furnace the fibres experience a constantly increasing temperature between about room temperature and, for example, 1100 C. The total dwell time in the carbonisation furnace is between about 3 and 50 hours.
  • the carbonisation is preferably carried out in flowing hydrogen, to which about 0.5 to volume percent of water vapour are admixed for simultaneous etching away of the fibres during the carbonisation.
  • This gas mixture is advantageously blown into the carbonisation furnace on the same side as that where the fibres are drawn into the furnace.
  • Inert gases can additionally also be admixed to the hydrogen-water vapour mixture.
  • the liquid is contained in a trough which is closed gastight by means of a lid.
  • the lid possesses an orifice through which the fibres are passed into the liquid.
  • the orifice is matched to the fibre product, namely individual fibre or filament, fibre strip consisting of many thousand individual fibres, yarn, woven fabric, knitted fabric or fleece. It should not be unnecessarily large, so as to keep the evaporation of the liquid low.
  • a tube attachment which is mounted gastight at the inlet into the carbonisation furnace, projects into the liquid from above.
  • the fibre material is passed by means of direction-changing rollers or guide rollers shrough the liquid into the tube attachment and into the carbonisation furnace.
  • the arrangement of the trough and of the tube attachment are so chosen that the liquid cannot run out of the trough into the furnace.
  • Possible liquids are water and all liquid substances containing water which release water vapour at room temperature or at the temperatures used for the carbonisation.
  • the manufacture of thin carbon fibres by etching away will not be combined with simultaneous dosing of the fibres with elements which are not contained in the fibre starting material.
  • Liquids containing water which are particularly suitable for the process according to the invention are those which only contain elements from the class H, C, N and O, for example acids, alkalies, alcohols, aldehydes, ketones or hydrazine or hydrazine compounds. Hydrazine hydrate with hydrazine concentrations of between about 15 and 64% of N H is very suitable.
  • the procedure according to the invention will employ a liquid under normal pressure.
  • the temperature of the liquid is below 100 C., preferably between about 0 and about C. It is advisable to use a transparent trough (for example of thick-walled glass or plastic) and transparent liquids, so that the fibre material can be observed at any time during its travel through the trough.
  • a transparent trough for example of thick-walled glass or plastic
  • transparent liquids so that the fibre material can be observed at any time during its travel through the trough.
  • the amount of liquid which passes into the carbonisation furnace depends on the following parameters:
  • the amount carried away depends on the viscosity of the liquid and on the specific surface area of the heat-treated fibres. The higher is the viscosity and the greater is the fibre surface, the more liquid is carried away into the furnace.
  • the surface of the fibres depends on the starting material and its geometry, and also on the heat treatment in the oxygen-containing atmosphere and is, in the BET determination, generally of the order of magnitude of m. /g.
  • replenishment of the components in which the liquid would otherwise become depleted must be provided. This can for example be done by allowing the components in question to run dropwise into the liquid.
  • the figure shows a device for carrying out the process.
  • the fibre product consisting of an acrylonitrile polymer, for example a fibre strip
  • the fibre product is drawn from the stock roll 1 possessing the brake drum 2 via the rollers 4 with the aid of the first pair of tension rollers 3 and the second pair of tension rollers 5, through the tubular furnace 6 possessing the quartz tube 7 and the funnels 8.
  • a defined amount of air is passed into the tube 7 via the regulator 8a.
  • the fibre strip is passed via the direction-changing roller 10 and through the funnel 18 into the trough 15 having a lid 16, and is passed via the direction-changing rollers 19, the dip tube 20 and the direction-changing rod 21 through the liquid 17 into the tubular furnace 12 having a quartz tube 13.
  • an oxygen-free gas is introduced via the regulator 12a.
  • the carbon fibre band is wound up on the roll 14.
  • EXAMPLE 1 An endless fibre strip consisting of 6000 individual fibres of acrylonitrile homopolymer, each of 1.8-1.9 dtex. is located on a stock roll 1, the extract of which is borne horizontally so that it can rotate. A brake drum 2 with variable adjustable braking action is seated on the axis. The fibre strip is continuously drawn from the stock roll between two vertical guide rods by means of a first pair of tension rollers 3 of which one roller is driven by a synchronous motor. Both rollers are cylindrical; their axes are arranged parallel to one another in a vertical plane. The driven, lower roller consists of mirror-polished high-quality alloy steel.
  • the upper roller is rubber-coated, borne so that it is rotatable about its axis, and is Pressed with adjustable firmness'against the drive roller, with the axes of both rollers remaining parallel.
  • adjustable firmness'against the drive roller with the axes of both rollers remaining parallel.
  • rollers 4 borne in two different horizontal planes, which on drawing the strip from the brakes stock roll convert the almost circular strip cross-section into a rectangular cross-section of large width and small height.
  • the heater winding of the furnace is so arranged that a constant temperature of 230 C. prevails over 80 cm. tube length and a gradual temperature rise of 4-5 C./cm. prevails at the furnace inlet side.
  • a quartz tube 7 of 5 cm. internal diameter is located in the furnace. Glass funnels 8 are cemented into the tube at both ends, and these ensure that the strip is axially guided through the furnace.
  • 50 1. (measured at N.T.P.) of air/hour are blown in via the regulator 8a,
  • the strip runs through the heat-treatment furnace at a speed of 17 cm./hour.
  • the length of the strip is kept constant, whilst travelling through the heat-treatment furnace, by means of the two pairs of tension rollers at the inlet and outlet of the furnace.
  • the strip which leaves the heat-treatment furnace again has an almost circular cross-section, and this is converted by two rollers 9, borne in dilferent horizontal planes, into a rectangular cross-section of large width and small height, before the strip passes between the two tension rollers of the second pair. This results in uniform tension of the strip.
  • the strip is drawn vertically downwards via a direction-changing roller 10, in order to pass through the carbonisation furnace in a lower horizontal plane and in the converse direction (relative to the direction in the heat-treatment furnace).
  • a knife 11-inclined at about 45 to the horizontal plane- is located with the cutting edge tightly against the lower roller above the level of the axis. The strip slides over the inclined knife plane.
  • the carbonisation occurs in a 300 cm. long tubular furnace 12 which possesses ten separate adjacent heater windings, each of about 30 cm. length (in the direction of the axis of the tube). At the ends, each of the ten windings are wound more tightly to avoid subsidiary minima in the temperature profile.
  • Each winding is heated via its own variablev transformer, in such a way that a strictly monotonously rising temperature curve results along the axis of the tube between the inlet and outlet of the furnace.
  • the furnace inlet is at 150 C.
  • the maximum temperature which is reached shortly before the furnace outlet, is 1050" C.
  • a quartz tube 13 of 5 cm. internal diameter and smooth glazed internal wall lies in the furnace. The strip is drawn through this tube by means of a winding machine 14 with a cycling drive and slipping clutch.
  • the carbonisation takes place in a stream of hydrogen (100 1. measured at N.T.P. H /hour).
  • the hydrogen is introduced via the regulator 12a at the same end of the furnace as the strip, but through a separate orifice. Excess hydrogen and reaction vapours leave the furnace at the other end, together with the carbonised strip.
  • a glass trough 15 with a lid 16 contains 2.5 l. of water as the liquid 17.
  • distilled water at room temperature is used.
  • the strip is guided through a glass funnel 18 set in the lid 16 into the water and is drawn via two direction-changing rollers 19 of polished high quality alloy steel through a glass tube 20 of 8 mm. internal diameter and having rounded edges, which dips into the water, and over a glass rod 21 arranged horizontally at the level of the tubular furnace axis and at right angles to the axis, axially through the carbonisation furnace.
  • the glass funnel 18 and the glass tube 20 are set in the lid 16 in a gas-tight manner; the lid is connected to the trough 15 in a gas-tight manner.
  • the consumption of water is 2.4 ml./hour.
  • the carbon fibre strip manufactured in this way has a completely smooth, glossy appearance, and is very flexible and also suitable for textile applications. It has a C content of 97%.
  • the average cross-section of the carbonised individual fibres is 20.10 cm.
  • the specific resistance has a value of 17.10*S2.cm.
  • the tensile strength was measured to be 1.5.10 kg. f./cm. and the modulus of elasticity 2.4.10 kg. f./cm.
  • EXAMPLE 2 An endless fibre strip consisting of 3000 individual fibres of acrylonitrile homopolymer, each of 2.4 dtex, is heattreated and carbonised in the installation shown in FIG. 1.
  • the three synchronous motors which drive the two pairs of tension rollers 3 and 5 and the Winding machine 14 were replaced by three synchronous motors which each run at twice the speeds compared to Example 1.
  • the maximum temperature was raised to 250 C.; this temperature is constant over a tube length of 77 cm. (in Example 1, 230 C. is constant over 80 cm. tube length).
  • the liquid 17 consists here of an 80% strength aqueous solution of hydrazine hydrate at room temperature.
  • the heat treatment time and the carbonisation time are reduced to half relative to Example 1.
  • the consumption of liquid 17 is here 1.9 ml./hour. All other conditions are exactly as has been described in Example 1.
  • the carbon fibre strip manufactured in this manner has a C content of 96.5%.
  • the average cross-section of the individual fibre is 45.10- cm. and the specific electrical resistance is 20.10 9cm.
  • the tensile strength has a value of 1.31.10 kg. f./cm. and the modulus of elasticity was found to be 2.7.10 kg. f./cm.
  • An endless fibre strip consisting of 5000 untwisted individual fibres of acrylonitrile homopolymer, each of 1.5 to 1.6 dtex, is heat-treated and carbonised exactly as described in Example 2, with the sole difference that the liquid 17 consists of a mixture of acetic acid and water in the molecular ratio of 1:1, at room temperature.
  • the consumption of liquid is 3.3 mL/hour.
  • a carbon fibre strip having the following properties is obtained:
  • An endless fibre strip consisting of 8000 untwisted individual fibres of acrylonitrile homopolymer, each of 2.0 dtex, is heat-treated and carbonised as described in Example 2, but making the following changes: items 15 to 19 and item 21 are omitted.
  • the tube attachment 20 here has an internal diameter of 2.5 mm. and is arranged coaxially to the axis of the tubular furnace 12.
  • a mixture of hydrogen and water vapour is here blown in through the attachment sketched at right angles to the tubular axis of the furnace 12, 100 1. (measured at N.T.P.) of H /hour and 10 1. (measured at N.T.P.) of H vapour/ hour being used.
  • the carbonisation was also carried out without water vapour.
  • the invention also provides equipment for carrying out the process comprising the sequence of a stock roll, a pair of tension rollers at opposite ends of a tubular furnace, a trough with a lid for containing water or a water containing liquid, a further tubular furnace connected to the trough through a dip tube and the second tubular furnace being followed by a wind-up roll.
  • a knife is mounted on the lower roller of the pair of tension rollers at the outlet end of the first tubular furnace.
  • a process according to claim 2 carried out as a continuous process.
  • aqueous liquid does not contain compounds of elements other than hydrogen, carbon, nitrogen, and oxygen.
  • aqueous liquid contains an acid, an alkali, an alcohol, an aldehyde, a ketone, a hydrazine or a hydrazine compound.

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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)
US00123368A 1970-03-14 1971-03-11 Process for producing carbon fibres Expired - Lifetime US3769390A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE19702012284 DE2012284A1 (de) 1970-03-14 1970-03-14 Verfahren zur Herstellung von Faser-Produkten mit dünnen Kohlenstoffasern

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US (1) US3769390A (de)
BE (1) BE764118A (de)
CA (1) CA960011A (de)
CH (1) CH515185A (de)
DE (1) DE2012284A1 (de)
FR (1) FR2084597A5 (de)
GB (1) GB1311817A (de)
NL (1) NL7103350A (de)
SU (1) SU438171A3 (de)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3928520A (en) * 1971-08-19 1975-12-23 Pilot Kiko Kk Black lead and production thereof
US3976746A (en) * 1974-06-06 1976-08-24 Hitco Graphitic fibers having superior composite properties and methods of making same
US4118341A (en) * 1974-05-27 1978-10-03 Agency Of Industrial Science & Technology Activated carbon
US4534919A (en) * 1983-08-30 1985-08-13 Celanese Corporation Production of a carbon fiber multifilamentary tow which is particularly suited for resin impregnation
US4714642A (en) * 1983-08-30 1987-12-22 Basf Aktiengesellschaft Carbon fiber multifilamentary tow which is particularly suited for weaving and/or resin impregnation
US4781223A (en) * 1985-06-27 1988-11-01 Basf Aktiengesellschaft Weaving process utilizing multifilamentary carbonaceous yarn bundles
US4919860A (en) * 1986-06-25 1990-04-24 Akzo Nv Manufacture of porous carbon membranes
WO2007093582A1 (de) * 2006-02-15 2007-08-23 Bayer Technology Services Gmbh Katalytisches ätzen von kohlenstofffasern
US20090277772A1 (en) * 2006-04-15 2009-11-12 Toho Tenax Co., Ltd. Process for Continous Production of Carbon Fibres
US20110104489A1 (en) * 2007-10-11 2011-05-05 Toho Tenax Co., Ltd. Hollow carbon fibres and process for their production

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4559010A (en) * 1984-05-01 1985-12-17 Toray Industries, Inc. Apparatus for producing oxidized filaments
US4776995A (en) * 1985-03-22 1988-10-11 Fiber Materials, Inc. Method of making a structure

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3928520A (en) * 1971-08-19 1975-12-23 Pilot Kiko Kk Black lead and production thereof
US4118341A (en) * 1974-05-27 1978-10-03 Agency Of Industrial Science & Technology Activated carbon
US3976746A (en) * 1974-06-06 1976-08-24 Hitco Graphitic fibers having superior composite properties and methods of making same
US4534919A (en) * 1983-08-30 1985-08-13 Celanese Corporation Production of a carbon fiber multifilamentary tow which is particularly suited for resin impregnation
US4714642A (en) * 1983-08-30 1987-12-22 Basf Aktiengesellschaft Carbon fiber multifilamentary tow which is particularly suited for weaving and/or resin impregnation
US4781223A (en) * 1985-06-27 1988-11-01 Basf Aktiengesellschaft Weaving process utilizing multifilamentary carbonaceous yarn bundles
US4919860A (en) * 1986-06-25 1990-04-24 Akzo Nv Manufacture of porous carbon membranes
WO2007093582A1 (de) * 2006-02-15 2007-08-23 Bayer Technology Services Gmbh Katalytisches ätzen von kohlenstofffasern
US20090047207A1 (en) * 2006-02-15 2009-02-19 Bayer Technology Services Gmbh Catalytic etching of carbon fibers
US7638111B2 (en) 2006-02-15 2009-12-29 Bayer Technology Services Gmbh Catalytic etching of carbon fibers
US20100021368A1 (en) * 2006-02-15 2010-01-28 Bayer Technology Services Gmbh Catalytic etching of carbon fibers
CN101384758B (zh) * 2006-02-15 2011-08-03 拜尔技术服务有限责任公司 碳纤维的催化蚀刻
US8354089B2 (en) 2006-02-15 2013-01-15 Bayer Technology Services Gmbh Catalytic etching of carbon fibers
US20090277772A1 (en) * 2006-04-15 2009-11-12 Toho Tenax Co., Ltd. Process for Continous Production of Carbon Fibres
US20110104489A1 (en) * 2007-10-11 2011-05-05 Toho Tenax Co., Ltd. Hollow carbon fibres and process for their production

Also Published As

Publication number Publication date
CA960011A (en) 1974-12-31
FR2084597A5 (de) 1971-12-17
BE764118A (fr) 1971-08-02
GB1311817A (en) 1973-03-28
DE2012284A1 (de) 1971-10-07
NL7103350A (de) 1971-09-16
CH515185A (de) 1971-11-15
SU438171A3 (ru) 1974-07-30

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